Article

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Sequential Carbon−Carbon/Carbon−Selenium Bond Formation

Mediated by Iron(III) Chloride and Diorganyl Diselenides: Synthesis
and Reactivity of 2‑Organoselenyl-Naphthalenes
Ana M. S. Recchi,† Davi F. Back,‡ and Gilson Zeni*,†
†
Laboratório de Síntese, Reatividade, Avaliaçaõ Farmacológica e Toxicológica de Organocalcogênios and ‡Laboratório de Materiais
Inorgânicos, CCNE, UFSM, Santa Maria, Rio Grande do Sul 97105-900, Brazil
*
S Supporting Information
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ABSTRACT: In this paper, we report an intramolecular

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cyclization of benzylic-substituted propargyl alcohols pro-

moted by iron(III) chloride and diorganyl diselenides to give
2-organoselenyl-naphthalenes via a sequential carbon−carbon/
carbon−selenium bond formation. The present reaction tolerated a wide range of substituents in both propargyl alcohols and
diorganyl diselenides to give the desired 2-organoselenyl-naphthalenes in good yields with high selectivity. In addition, O-acyl
protected propargyl alcohol and propargyl bromide were also subjected to this protocol giving the corresponding 2-
organoselenyl-naphthalenes. We found that dichalcogenide species affected the formation of cyclized products, whereas diorganyl
diselenides gave high yields, moderate yields were obtained with diorganyl disulfides, and no product formation was found with
diorganyl ditellurides. The key transformations could be attributed to the carbon−carbon triple bond activation of benzylic-
substituted propargyl alcohols by a seleniranium ion, antiattack of the electron cloud from the aromatic ring at the activated triple
bond, and cyclization via an exclusive 6-endo-dig process. We also found that the corresponding 2-organoselenyl-naphthalenes are
suitable substrates to the selenium−lithium exchange reactions followed by trapping with aldehydes affording the corresponding
secondary alcohols.

■ INTRODUCTION
The initial observations that selenium prevents liver necrosis in
synthesis of a variety of substituted organoselenium compounds
from readily accessible starting materials under mild con-
rats fed a selenium-deficient Torula yeast in the early 1950s1 ditions.10 Iron reagents have appeared as an attractive
and its molecular function in mammalian cells led to alternative to other transition metals because their relative
demonstration that selenium is a nutritionally important trace stability, abundance, low toxicity, economic and ecologic
element.2 The detection of selenocysteine in the active center advantages, and excellent tolerance toward various functional
of hepatic rat glutathione peroxidase confirmed the existence of groups.11 The iron(III)-catalyzed annulation reactions are
a new nucleophile, the selenolate.3 These studies had a decisive particularly efficient strategy for the naphthalene derivatives
contribution to change the view of researchers about selenium construction.12 The importance of naphthalenes derives from
chemistry.4 As a result, intense interest has been directed their well-known physical, chemical13 and biological proper-
toward the development of new methods for the synthesis of ties.14 The previous investigation of Larock and co-workers
organoselenium compounds, and a variety of well-established utilized PhSeBr as electrophilic source in the cyclization
classical methods to introduce a selenium moiety in organic reaction of alkynols 1, aiming at introducing PhSe at 2-position
substrates are now available in the literature.5 One of the ways of naphthalene rings.15 However, the reaction afforded the
to access organoselenium compounds is the transformation of desired product in a modest 36% yield together with the
elemental selenium into nucleophilic species by reaction with product of PhSeBr addition to alkyne 3 in 53% yield. In order
lithium and Grignard reagents or by reduction of diorganyl to introduce an organoselenium moiety at the 2-position of
diselenides by alkali metals or alkali hydrides.6 Other common naphthalene rings, in a one-step reaction, we explored if
approach to introduce a selenium moiety into organic alkynols 1 can be used as starting materials to prepare 2-
molecules involves the use of selenium electrophilic species,
organoselenyl-naphthalenes 2, instead of vinylic selenides 3, in
which can be easily prepared by reaction of diorganyl
a cyclization reaction promoted by diorganyl diselenides and
diselenides with a halogen source,7 although nowadays they
are commercially available. Further important methods include iron salts (Scheme 1). From a synthetic point of view,
the use of selenium radical species, which can be obtained by molecules having a C(sp)2-Se bond have been extensively
homolytic cleavage of the selenium−selenium single bond using modified for selective construction of more complex structures
irradiation with light near-UV region.8 Organoselenyl radicals via carbon−carbon bond formation.16
thus formed exhibit high reactivity toward other substrates.9 In
recent years, the concept of combining iron salts with diorganyl Received: January 9, 2017
diselenides has emerged as a promising strategy for the Published: February 14, 2017

© 2017 American Chemical Society 2713 DOI: 10.1021/acs.joc.7b00050

J. Org. Chem. 2017, 82, 2713−2723
The Journal of Organic Chemistry Article

Scheme 1

Table 1. Effect of Different Reaction Parameters on the Preparation of 2-(Phenylselanyl)-naphthalene 2aa

entry PhSeSePh (equiv) promoter (equiv) solvent temperature (°C) yield (%)b
1 1.5 FeCl3 (1.5) CH2Cl2 40 71
2 1.5 BF3OEt2 (1.5) CH2Cl2 40 37
3 1.5 ZnCl2 (1.5) CH2Cl2 40 N.R.
4 1.5 PTSA (1.5) CH2Cl2 40 16
5 1.5 H3PO4 (1.5) CH2Cl2 40 N.R.
6 1.5 FeCl3 (1.5) CH2Cl2 25 60
7 0.75 FeCl3 (1.5) CH2Cl2 40 55
8 0.6 FeCl3 (1.5) CH2Cl2 40 77
9 0.6 FeCl3 (1.5) CH2Cl2 40 77c
10 0.6 FeCl3 (2.0) CH2Cl2 40 67
11 0.6 FeCl3 (1.5) CH2Cl2 40 67
12 0.6 FeCl3 (1.5) DCE 70 63c
13 0.6 FeCl3 (1.0) DCE 70 59
14 0.6 FeCl3 (1.0) DCE 70 56c
15 0.6 FeCl3 (0.5) DCE 70 69
16 0.6 FeCl3 (0.75) DCE 70 71c
17 0.6 FeCl3 (0.3) CH2Cl2 40 11
18 0.6 FeCl3 (0.3) CH2Cl2 40 42d
19 0.6 FeCl3 (0.3) DCE 70 50
20 0.6 FeCl3 (0.75) CHCl3 60 65c
21 0.6 FeCl3 (0.75) CH3CN 82 64c
22 0.6 FeCl3 0.75 toluene 110 45c
23 0.6 FeCl3 (0.75) CH3NO2 100 27c
24 0.6 FeCl3 0.75 EtOH 78 16c
25 0.6 FeCl3 (0.75) THF 67 15c
26 0.6 FeCl3 (0.75) 1,4-dioxane 100 10c
27 0.6 FeCl3·6H2O (0.75) DCE 70 51c
28 0.6 FeSO4·7H2O (0.75) DCE 70 >5c
29 0.6 Fe(acac)3 (0.75) DCE 70 >5c
30 0.6 FeCl2·4H2O (0.75) DCE 70 29c
31 0.6 Fe2O3 (0.75) DCE 70 N.R.c
32 0.6 FeCl3 (0.75) DCE 70 77e
33 0.6 FeCl3 (0.75) DCE 70 56c,e,f
34 0.6 − DCE 70 N.R.
a
The reaction was performed by addition of diphenyl diselenide to a solution of promoter in solvent (5 mL), under argon atmosphere at room
temperature. After 15 min at this temperature, alkynol 1a (0.25 mmol) was added. The resulting mixture was stirred under temperature indicated in
the table for 12 h. bYield of purified product. cThe reaction was carried out under air atmosphere in an open flask. dThe reaction was performed with
K2CO3 (2 equiv). eThe resulting mixture was stirred for 1 h. fThe reaction was performed with DCE (2 mL).

■ RESULTS AND DISCUSSION

General Conditions. The starting alkynols 1 used for the
carried out by addition of diorganyl diselenide (1.5 equiv) to a
solution of the promoter (1.5 equiv) in dichloromethane (5
mL), under argon atmosphere at room temperature. After 15
synthesis of 2-organoselenyl-naphthalenes 2 are easily acces-
min at this temperature, the alkynol 1a (0.25 mmol) was added
sible from alkynylation of commercially available carbonyl and the reaction was heated to reflux. Among the Lewis acid
compounds using lithium acetylides as the alkynylating agent. tested, that with iron(III) chloride gave the 2-phenyselenyl-
Initial investigations for the cyclization of alkynols 1 were made naphthalene 2a in a higher yield (Table 1, entries 1−3). Further
using diphenyl diselenide as organoselenium source and a investigations indicated that the Bronsted acids tested were
Bronsted or a Lewis acid as promoter. Thus, the cyclization was ineffective in promoting the cyclization of alkynol 1a (Table 1,
2714 DOI: 10.1021/acs.joc.7b00050
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The Journal of Organic Chemistry Article

entries 4 and 5). These results are in agreement with previously tion and 5-exo-dig mode resulting in a mixture of isomers. The
report that iron salts are the most efficient Lewis acid for regiochemical outcome of the carbon attack was based on
selenium−selenium bond cleavage under proper condi- NMR analysis and proved by single-crystal X-ray diffraction of
tions.10d,17 Because the high yield obtained for the cyclization the 2-phenyselenyl-naphthalene 2a, which confirmed that the
of alkynol 1a, iron(III) chloride was shown to be the promoter reaction followed a 6-endo-dig process (Figure 1; the CCDC
of choice for additional optimization studies. Decreasing the 1525289 contains the supplementary crystallographic data for
reaction temperature to 25 °C led to the formation of 2a in the compound 2a).
60% yield together with the starting material (Table 1, entry 6).
Next, our experimental protocol turned to the effect of diphenyl
diselenide amount. The decrease in the amount of diphenyl
diselenide to 0.75 gave the product in moderate yield, while the
reduction to 0.6 equiv led to obtain 2a in 77% yield (Table 1,
entries 7 and 8). The use 0.6 equiv implies that both portions
(2 PhSe) of diphenyl diselenide (PhSeSePh) are incorporated
into the structure of the final product. This is important
because the atom economy obtained results in a reduction in
the quantity of waste and unwanted byproducts delivering Figure 1. Competition between the intramolecular 6-endo-dig (route
significant environmental benefits and cost savings. We carried a) cyclization and 5-exo-dig mode (route b).
out many experiments using open tube instead of inert
atmosphere (argon), to determine if the oxygen could be the Scope of the Reaction. With the optimization conditions
oxidizing agent for the regeneration of diphenyl diselenide determined, they were expanded to a wide variety of alkynols 1
(PhSeSePh) from selenol (PhSeH). These studies revealed that and diorganyl dichalcogenides and the results are shown in
the yield in the formation of 2a was not significantly modified Table 2. To investigate the influence of diorganyl diselenides on
using air atmosphere instead of inert atmosphere (argon), the synthesis of 2-organoselenyl-naphthalenes 2, we studied the
owing to economic or technical reasons, an open flask was reaction of alkynol 1a with diorganyl diselenides bearing
adopted for further studies (Table 1, entry 9). Additional different substituents on the structure (Table 2, entries 1−13).
investigations indicated that the cyclization proceeded When the alkynol 1a was reacted with diaryl diselenides
smoothly to give the 2-phenyselenyl-naphthalene 2a in good containing neutral or electron-donating groups on their aryl
yield even when the loading of iron(III) chloride was reduced moieties, the corresponding naphthalene derivatives 2a−e were
to 0.75 equiv (Table 1, entries 10−16). However, low yields obtained in good yields (Table 2, entries 1−5). An exception
were obtained when the reactions were performed in a catalytic for these series was observed for diaryl diselenide having a
amount of iron(III) chloride (Table 1, entries 17−19). To methoxyl group at the para position (Table 2, entry 6). In this
optimize the reaction medium, other solvents were examined. case no cyclization product was observed under the standard
Among the solvents tested, chloroform and acetonitrile conditions and a significant amount of the diaryl selenide 4 was
delivered good cyclization conversion, while with toluene, isolated together with alkynol 1a (Scheme 2, eq 1). The
nitromethane, ethanol, tetrahydrofuran and 1,4-dioxane lower generation of 4 could be explained in terms of iron selenol
yields of product were obtained (Table 1, entries 20−26). Next, formation, which could undergo further C−Se bond formation
other iron sources were considered under the cyclization by the coupling of selenol and diaryl diselenides.10d,18 To prove
conditions. The results obtained did not show any further this hypothesis we reacted the bis(4-methoxyphenyl) diselenide
improvement over the results obtained with iron(III) chloride with iron(III) chloride in the absence of alkynol 1a, under our
(Table 1, entries 27−31). We followed the progress of the standard reaction conditions (Scheme 2, eq 2). After 1 h we
reaction by periodic analysis using TLC to determine the obtained the bis(4-methoxyphenyl) selenide quantitatively as
necessary reaction time for the complete consumption of the the product. This result suggests that the reaction of alkynol 1a
starting material. We observed that 1.0 h was the required time with bis(4-methoxyphenyl) diselenide did not allow the
taken for the reaction to be completed (Table 1, entry 32). To cyclization even that using an excess of diselenide, reflux and
minimize the amount of waste solvents, we tested the effect of a long reaction time, because the diselenide is consumed in a
concentration on the yield of reaction and good yields were still parallel reaction with iron salt (Scheme 2). Under the
achieved using 2.0 mL of DCE instead of 5.0 mL (Table 1, optimized reaction conditions, the diaryl diselenides containing
entry 33). These last two experiments are significant because electron-withdrawing groups gave good results on the
makes the present cyclization more economical and environ- cyclization of alkynol 1a but with lower yields than those of
mentally attractive in terms of energy efficiency. When we run diaryl diselenides containing electron-donating groups (Table
the reaction of alkynol 1a with diphenyl diselenide, in the 2, entries 7−9). In addition, the bulky diaryl diselenides gave
absence of iron(III) chloride, 2-phenyselenyl-naphthalene 2a the cyclized products 2j and 2k in moderate yields (Table 2,
was not obtained and only the starting material was recovered entries 10 and 11), suggesting that electronic and steric effects
(Table 1, entry 34). The evaluation of reaction conditions of substituents on the diselenides influence the yields of this
studied showed that the addition of alkynol 1a (0.25 mmol) to cyclization process. The electronic and steric effects can restrict
a previous prepared solution of diphenyl diselenide (0.6 equiv) the selenium−selenium bond cleavage by iron salt. The
and iron(III) chloride (0.75 equiv) in DCE (2 mL), under air reaction was therefore investigated using heteroaryl diselenides,
atmosphere at 70 °C for 1 h, is the best condition to obtain the such as bis(pyridyl) diselenide and bis(thienyl) diselenide;
2-phenyselenyl-naphthalene 2a in higher yield (Table 1, entry however, they failed to provide the desired naphthalene
33). The distance between the nucleophilic carbon of the products (Table 2, entries 12 and 13). These negative results
aromatic ring and the carbon−carbon triple bond could result can be rationalized through the coordination of donor atoms of
in competition between the intramolecular 6-endo-dig cycliza- the heteroaryl diselenides with iron chloride giving an iron
2715 DOI: 10.1021/acs.joc.7b00050
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The Journal of Organic Chemistry Article

Table 2. Synthesis of 2-Organoselenyl-naphthalenes 2a

2716 DOI: 10.1021/acs.joc.7b00050

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The Journal of Organic Chemistry Article

Table 2. continued

a
The reaction was performed by the addition of diorganyl dichalcogenide (0.6 equiv) to a solution of FeCl3 (0.75 equiv) in DCE (2 mL), under air
atmosphere, at room temperature. After 15 min, at this temperature, alkynol 1 (0.25 mmol) was added. The resulting mixture was stirred at 70 °C for
the time indicated in Table 2. bThe reaction was performed using diorganyl diselenide (1.5 equiv) and FeCl3 (1.5 equiv). cThe reaction was
performed using FeCl3 (1.5 equiv). d(MeS)2 (8 equiv) was used. eK2CO3 (2 equiv) was used.

Scheme 2

Scheme 3

stable complex hampering the cyclization. We next examined showed to be sensitive to the presence of bulky naphthalene
the cyclization reaction of the substituted alkynols 1b−j, each group giving the products 2u and 2v only in moderate yields
one bearing a substituent at the aromatic ring directly bonded (Table 2, entries 21 and 22). We next examined the cyclization
to the triple bond (Table 2, entries 14−22). We reacted of alkynols with a methyl group at the homopropargyl and
alkynols bearing methyl and methoxyl groups with diphenyl propargyl positions. With these substrates we observed no
diselenide in order to investigate the influence of electron- difference in reactivity, whereas the reactions could be
donating groups on the aromatic ring. In all cases the performed at 70 °C for 1 h affording 2x and 2y in 68 and
corresponding organoselenyl-naphthalenes were obtained in 65% yields, respectively (Table 2, entries 23 and 24). With
high yields although, the alkynol 1b, which has a bulky methyl regard to the presence of substituents at the benzylic group,
group at the ortho-position, gave the desired product in methyl and methoxyl groups lead to better yields than that of
moderate yields (Table 2, entries 14−18). The alkynol 1e, the electron withdrawing chlorine group (Table 2, entries 24−
which has the methoxyl and the aromatic ring competing as 26). Replacing the diaryl diselenides by dialkyl diselenide had
potential nucleophiles, could gave the naphthalene 2q, no negative effect on the yield, as the cyclization reaction of
benzofuran 5 or a mixture of them (Scheme 3). The ratio of alkynol 1a with dibutyl diselenide gave the 2-butylselenyl-
products depends on several factors, including the nucleophilic naphthalene 2ab in 70% yield (Table 2, entry 27). The
character, the steric effects and polarization of the alkyne triple cyclization reaction of alkynol 1o, which has an alkyl chain
bond.19 Using our protocol, the cyclization of alkynol 1e gave bonded to alkyne was also investigated (Table 2, entry 28). It is
the exclusive formation of product, resulting from participation well recognized in the literature that this reaction could be
of phenyl ring as nucleophile. This result is in agreement with hampered when alkyl-substituted triple bonds are employed in
the higher nucleophilicity of phenyl ring when compared to electrophilic cyclization reaction.21 This reaction could only
that of the methoxyl group.20 The effects of electron give a moderate yield of cyclized product or in some cases the
withdrawing and bulky groups directly bonded to alkyne were product of triple bond reduction was isolated as the exclusive
also studied. When we used alkynol 1g, which has chlorine at product. This last product probably arises from the addition of
the para-position of this aromatic group, the cyclized product electrophilic species to the carbon−carbon triple bond.7 The
was obtained in 80% yield, whereas the presence of fluorine hypothesis that the absence of π bonds next to the alkyne
substituent at the para-position gave the naphthalene in a decreased the reactivity of the carbon−carbon bond is
moderate 47% yield (Table 2, entries 19 and 20). The reaction considered to explain the behavior of this substrate. However,
2717 DOI: 10.1021/acs.joc.7b00050
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The Journal of Organic Chemistry Article

under our conditions the reaction of alkynol 1o with diphenyl (iii) The reaction running by sequential addition of all reagents,
diselenides gave the naphthalene 2ac in 74% yield (Table 2, instead of previous mixture of iron(III) chloride and diphenyl
entry 28). In an effort to extend the optimized reaction diselenide, gave 2a in only 56% yield (Scheme 4, eq 3). The
conditions to other diorganyl dichalcogenides, alkynol 1o was experiments described in Scheme 4, eqs 1−3 suggest that a
reacted with diorganyl disulfides and diorganyl ditellurides. The selenium electrophilic species alone is unable to promote the
diorganyl disulfides, upon cyclization conditions, afforded the cyclization reaction and that the mutual action between
products in moderate yields, whereas diorganyl ditellurides did iron(III) chloride and diphenyl diselenide is essential for the
not afford the products (Table 2, entries 29−32). The reactivity formation of 2a in good yield. (iv) No reaction occurred when
of disulfides in this cyclization reaction can be rationalized diphenyl diselenide was added to a previous prepared solution
through the strength of the sulfur−sulfur bond that prevents its of iron(III) chloride and alkynol 1a (Scheme 4, eq 4). This
cleavage by iron salt. The negative results obtained for experiment implies that a C(sp)2-Fe intermediated might not
ditellurides are probably explained by the formation of be the active species to promote cyclization of alkynol 1a. (v)
polymeric iron tellurolate complex, which is very instable, The reaction of alkynol 1a with diphenyl diselenide in the
decomposing via telluroxide elimination by oxidation.17 Besides presence of dry HCl gas and the absence of iron(III) chloride
the alkynol, O-acyl and bromine groups at the propargyl led to a complex mixture of unidentified products (Scheme 4,
position could also react well under the optimized reaction eq 5). This result excludes the action of HCl, released from
conditions to give the 2-phenylselenyl-naphthalenes 2a in decomposition of iron(III) chloride, as a cyclization promoter.
moderate yields (Table 2, entries 33 and 34). vi) Upon adding radical inhibitors, such as TEMPO and
Mechanism Discussion. To establish a plausible reaction hydroquinone, the reaction of alkynol 1a with diphenyl
mechanism, a number of control reactions were performed diselenide, under optimized reaction conditions gave the
(Scheme 4): (i) Treatment of alkynol 1a with PhSeCl, a product 2a in 65% and 82% yields respectively, which suggests
that a radical pathway does not contribute for the formation of
Scheme 4 2a (Scheme 4, eq 6). (vii) The reaction of alkynol 1a with
diphenyl diselenide using Cu2O 3 mol %, 5 mol %, 10 mol %
and 2 equiv as promoter did not result in conversion into the
desired product (Scheme 4, eq 7). These studies confirm that
iron(III) chloride is the real reactive species under the reaction
conditions and that the active participation of Cu2O as trace
contaminant of the iron(III) chloride is discarded.22
Mechanism Proposal. On the basis of above investigation
and the knowledge that iron salts react with diorganyl
diselenides promoting the selenium−selenium bond heteroge-
neous cleavage to give an organoselenyl cation and an
organoselenyl anion,10d,17 a plausible mechanism for this
reaction has been outlined in Scheme 5. The coordination of

Scheme 5

the carbon−carbon triple bond to the electrophilic portion of

diphenyl diselenide generates the intermediate I. The iron(III)
coordination with one selenium atom from diorganyl diselenide
activates the other toward nucleophilic attack by the alkyne
giving the seleniranium ion II. The antiattack of the electron
cloud from the aromatic ring at the activated intermediate II
produces the cyclized cationic intermediate III via a 6-endo-dig
process. Deprotonation of intermediate III by selenolate anion
selenium electrophilic species that could be formed in situ by restores the aromatic ring giving the dihydronaphthalene
reaction of diphenyl diselenide with iron(III) chloride, afforded species IV, which can undergo dehydration to give 2-
the desired 2-phenyselenyl-naphthalene 2a in 38% yield, phenyselenyl-naphthalenes 2 (Scheme 5).
together with product of PhSeCl addition to alkyne (Scheme Reactivity of 2-Organoselenyl-Naphthalenes. The
4, eq 1).15 (ii) Treatment of alkynol 1a with PhSeCl and presence of C(sp)2-Se bond on the organic substrates offers
iron(III) chloride under the optimized conditions delivered the considerable potential for further elaboration, particularly in the
corresponding naphthalene 2a in 72% yield (Scheme 4, eq 2). formation of new carbon−carbon, carbon−metal, carbon−
2718 DOI: 10.1021/acs.joc.7b00050
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The Journal of Organic Chemistry Article

halogen and carbon−heteroatom formation via lithium selenium bonds were formed in a one step, this method
intermediate23 or applied as electrophiles in transition metal could be considered an economic and eco-friendly protocol.
catalyzed reactions.24 In this respect, the 2-organoselenyl- The other advantage of this protocol is that the reaction gave
naphthalenes prepared is a straightforward option to regio- and the products in good yields, using 0.6 equiv of diorganyl
stereoselectivity modification on naphthalene structures. To diselenides, which indicates that the two portions of diselenides
determine the reactivity of 2-organoselenyl-naphthalenes we were incorporated in the final products, demonstrating a high
envisioned that they could be treated with n-butyllithium to atom economy and conversion efficiency of the cyclization
give lithium naphthalenide anion, via selenium−lithium reactions.

■
exchange reactions, which would be trapped with aldehydes
to furnish the corresponding alcohols. Thus, organolithium EXPERIMENTAL SECTION
intermediate was generated by addition of n-butyllithium (1.1
equiv) to a solution of 2-organoselenyl-naphthalene (0.25 Materials and Methods. Proton nuclear magnetic resonance
spectra (1H NMR) were obtained on a NMR spectrometer at 400
mmol) in THF (5 mL) and hexane (5 mL), at room MHz. Spectra were recorded in CDCl3 solutions. Chemical shifts are
temperature. The resulting solution was stirred for 10 min at reported in ppm, referenced to the solvent peak of CDCl3 or
this temperature and the aldehyde was added at 0 °C and tetramethylsilane (TMS) as the external reference. Data are reported
reacted at room temperature for the time indicated in Scheme as follows: chemical shift (δ), multiplicity, coupling constant (J) in
6. The reactivity of different aldehydes having electron- Hertz and integrated intensity. Carbon-13 nuclear magnetic resonance
spectra (13C NMR) were obtained on a 400 NMR spectrometer at 100
Scheme 6 MHz. Spectra were recorded in CDCl3 solutions. Chemical shifts are
reported in ppm, referenced to the solvent peak of CDCl3.
Abreviations to denote the multiplicity of a particular signal are s
(singlet), d (doublet), t (triplet), quart (quartet), quint (quintet), sex
(sextet), dd (double doublet) and m (multiplet). High resolution mass
spectra were recorded on a mass spectrometer using electrospray
ionization (ESI). Column chromatography was performed using Silica
Gel (230−400 mesh). Thin layer chromatography (TLC) was
performed using Gel GF254, 0.25 mm thickness. For visualization,
TLC plates were either placed under ultraviolet light, or stained with
iodine vapor, or acidic vanillin. Most reactions were monitored by
TLC for disappearance of starting material. The following solvents
were dried and purified by distillation from the reagents indicated:
tetrahydrofuran from sodium with a benzophenone ketyl indicator. All
other solvents were ACS or HPLC grade unless otherwise noted. Air-
and moisture-sensitive reactions were conducted in flame-dried or
oven-dried glassware equipped with tightly fitted rubber septa and
under a positive atmosphere of dry nitrogen or argon. Reagents and
solvents were handled using standard syringe techniques. The FeCl3
was used in 99.99% purity purchased from commercial suppliers.
General Procedure for the Synthesis of 2-Organoselenyl-
naphthalenes 2a−ag. To a 10 mL Schlenk tube with a magnetic
stirring bar, at room temperature were charged FeCl3 (0.03 g, 0.18
withdrawing and electron-donating substituents on the
mmol), diorganyl dichalcogenides (0.15 mmol) and 1,2-dichloro-
aromatic ring afforded moderate to good yields of the desired ethane (3 mL). The reaction mixture was stirred at room temperature
secondary alcohols 6a−c. The 3-phenylpropiolaldehyde was for 15 min. After this time, appropriate substrate 1 (0.25 mmol) was
also suitable electrophile giving 6d in 48% yield. The reaction added and the reaction was stirred at 70 °C for the time indicated in
of lithium naphthalenide anion with DMF under the reaction Table 2. The mixture was dissolved in ethyl acetate, washed with a
conditions, gave the corresponding aldehyde 6e in 52%, after saturated solution of NH4Cl, dried with MgSO4, and concentrated in
16 h. vacuum. The residue was purified by column chromatography over

■ CONCLUSION
In summary, we have developed a strategy for the construction
silica gel to provide the products 2.
Phenyl(1-phenylnaphthalen-2-yl)selane 2a. Title compound was
isolated by column chromatography (hexane was eluent) as a light
yellow solid. Yield: 0.069 g (77%); mp 100−101 °C. 1H NMR
and functionalization of naphthalene rings by a sequential (CDCl3, 400 MHz) δ (ppm) 7.81−7.76 (m, 1H), 7.66−7.61 (m, 1H),
carbon−carbon/carbon−selenium bond cyclization of benzylic- 7.53−7.38 (m, 7H), 7.37−7.24 (m, 7H). 13C{1H} NMR (CDCl3, 100
substituted propargyl alcohols mediated by iron(III) chloride MHz) δ (ppm) 139.9, 139.7, 135.0, 133.2, 132.3, 131.0, 130.7, 130.2,
and diorganyl diselenides. The substrate scope of the reaction 129.4, 128.5, 128.3, 128.2, 127.9, 127.8, 126.5, 126.2, 125.5. MS (EI,
was studied, showing that a range of benzylic-substituted 70 eV; m/z (relative intensity)) 362 ([M + 2], 14), 360 (63), 280
propargylic alcohols were compatible with the optimized (60), 202 (100), 126 (03), 77 (09). HRMS calcd for C22H17Se (ESI-
reaction conditions, giving exclusively the 2-organoselenyl- TOF, [M + H]+) 361.0495, found 361.0501.
naphthalenes in good yields following a 6-endo-dig process. The (1-Phenylnaphthalen-2-yl)(p-tolyl)selane 2b. Title compound was
isolated by column chromatography (hexane was eluent) as a yellow
2-organoselenyl-naphthalenes thus obtained further underwent
solid. Yield: 0.074 g (80%); mp 141.2−145.9 °C. 1H NMR (CDCl3,
the selenium−lithium exchange reactions with n-buthyllithium 400 MHz) δ (ppm) 7.79−7.73 (m, 1H), 7.64−7.58 (m, 1H), 7.54−
to give the lithium naphthalenide anion, which was trapped 7.27 (m, 10H), 7.25−7.19 (m, 1H), 7.13−7.06 (m, 2H), 2.34 (s, 3H).
with aldehydes furnishing the corresponding alcohols. Consid- 13
C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 139.7, 139.1, 138.2,
ering that iron salts are easily available commercially, not 135.6, 133.1, 132.1, 131.7, 130.3, 128.5, 128.0, 127.9, 127.8, 127.6,
expensive, relatively nontoxic and the reactions were carried out 126.5, 126.4, 126.0, 125.3, 21.2. MS (EI, 70 eV; m/z (relative
under open tube, and the carbon−carbon and carbon− intensity)) 376 ([M + 2], 9), 374 (53), 294 (49), 279 (36), 207 (08),

2719 DOI: 10.1021/acs.joc.7b00050

J. Org. Chem. 2017, 82, 2713−2723
The Journal of Organic Chemistry Article

202 (100), 176 (06) 91 (20). HRMS calcd for C23H19Se (ESI-TOF, Hz), 120.9 (q, J = 272.7 Hz). MS (EI, 70 eV; m/z (relative intensity))
[M + H]+) 375.0652, found 375.0660. 429 ([M + 1], 12), 428 (50), 348 (31), 282 (15), 203(51), 202 (100),
(1-Phenylnaphthalen-2-yl)(o-tolyl)selane 2c. Title compound was 176 (6). HRMS calcd for C23H16F3Se (ESI-TOF, [M + H]+)
isolated by column chromatography (hexane was eluent) as a light 429.0369, found 429.0373.
yellow viscous oil. Yield: 0.084 g (90%). 1H NMR (CDCl3, 400 MHz) Naphthalen-1-yl(1-phenylnaphthalen-2-yl)selane 2j. Title com-
δ (ppm) 7.80−7.74 (m, 1H), 7.64−7.57 (m, 1H), 7.55−7.45 (m, 4H), pound was isolated by column chromatography (hexane was eluent) as
7.44−7.29 (m, 5H), 7.27−7.19 (m, 2H), 7.15−7.05 (m, 2H), 2.30 (s, a brown solid. Yield: 0.052 g (51%); mp 98−100 °C. 1H NMR
3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 141.7, 139.7, 139.6, (CDCl3,. 400 MHz) δ (ppm) 8.25−8.21 (m, 1H), 7.91−7.86 (m, 2H),
136.4, 133.2, 132.1, 131.1, 130.8, 130.3, 130.0, 128.7, 128.5, 128.1, 7.85−7.82 (m, 1H), 7.73−7.69 (m, 1H), 7.59−7.53 (m, 2H), 7.52−
127.8, 127.8, 127.6, 126.7, 126.4, 126.0, 125.4, 22.7. MS (EI, 70 eV; m/ 7.30 (m, 10H), 6.94 (d, J = 8.7 Hz, 1H). 13C{1H} NMR (CDCl3, 100
z (relative intensity)) 376 ([M + 2], 21), 375 ([M + 1], 25)], 374 MHz) δ (ppm) 139.6, 138.8, 135.8, 134.9, 134.2, 133.2, 132.0, 131.4,
(100), 372 (54), 294 (13), 282 (18), 279 (14), 204 (69), 203 (68), 130.2, 129.9, 129.1, 128.7, 128.6, 128.3, 128.1, 128.0, 127.9, 127.3,
202 (90), 169 (11), 91 (15). HRMS calcd for C23H19Se (ESI-TOF, [M 127.0, 126.4, 126.4, 126.0, 125.9, 125.3. MS (EI, 70 eV; m/z (relative
+ H]+) 375.0652, found 375.0661. intensity)) 410 ([M + 2], 100), 409 (16), 408 (52), 330 (68), 329
Mesityl(1-phenylnaphthalen-2-yl)selane 2d. Title compound was (67), 253 (67), 202 (93). HRMS calcd for C26H19Se (ESI-TOF, [M +
isolated by column chromatography (hexane was eluent) as a yellow H]+) 411.0652, found 411.0665.
light solid. Yield: 0.084 g (84%); mp 112.5−116 °C. 1H NMR Naphthalen-2-yl(1-phenylnaphthalen-2-yl)selane 2k. Title com-
(CDCl3, 400 MHz) δ (ppm) 7.76−7.69 (m, 1H), 7.58−7.45 (m, 4H), pound was isolated by column chromatography (hexane was eluent) as
7.44−7.26 (m, 5H), 6.98 (s, 2H). 6.82 (d, J = 8.7 Hz, 1H), 2.37 (s, a brown solid. Yield: 0.06 g (60%); mp 96.9−100.1 °C. 1H NMR
6H), 2.30 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 143.8, (CDCl3, 400 MHz) δ (ppm) 8.05−7.99 (m, 1H), 7.83−7.69 (m, 4H),
139.8, 139.0, 138.0, 133.3, 132.0, 131.8, 130.1, 128.9, 128.6, 128.0, 7.63−7.58 (m, 1 H), 7.55−7.27 (m, 12H). 13C{1H} NMR (CDCl3,
127.9, 127.8, 127.8, 126.3, 125.5, 125.3, 124.9, 24.2, 21.0. MS (EI, 70 100 MHz) δ (ppm) 139.9, 139.7, 134.2, 134.1, 133.2, 132.7, 132.3,
eV; m/z (relative intensity)) 404 ([M + 2], 22), 403 ([M + 1], 28), 132.0, 131.0, 130.2, 128.8, 128.5, 128.4, 128.2, 128.0, 127.9, 127.9,
402 (100), 400 (56), 399 (22), 282 (11), 204 (32), 203 (40), 202 127.8, 127.6, 126.5, 126.4, 126.2, 125.5. MS (EI, 70 eV; m/z (relative
(63), 200 (25), 198 (67), 196 (33), 119 (25), 91 (18). HRMS calcd intensity)) 410 (73), 331 (21), 330 (77), 329 (57), 281 (18), 253
for C25H23Se (ESI-TOF, [M + H]+) 403.0965, found 403.0973. (14), 202 (100), 163 (15), 115 (17). HRMS calcd for C26H19Se (ESI-
(2-Methoxyphenyl)(1-phenylnaphthalen-2-yl)selane 2e. Title TOF, [M + H]+) 411.0652, found 411.0682.
compound was isolated by column chromatography (eluent 1% Phenyl(1-o-tolylnaphthalen-2-yl)selane 2n. Title compound was
EtOAc in hexane) as a light yellow viscous oil. Yield: 0.071g (73%). 1H isolated by column chromatography (hexane was eluent) as a light
NMR (CDCl3, 400 MHz) δ (ppm) 7.83−7.78 (m, 1H), 7.69−7.64 yellow viscous oil. Yield: 0.054 g (58%). 1H NMR (CDCl3, 400 MHz)
(m, 1H), 7.50−7.38 (m, 6H), 7.37−7.30 (m, 3H), 7.27−7.20 (m, 2H), δ (ppm) 7.81−7.76 (m, 1H), 7.67−7.61 (m, 1H), 7.56−7.51 (m, 2H),
6.87−6.78 (m, 2H), 3.76 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz) 7.44−7.36 (m, 3H), 7.35−7.21 (m, 7H), 7.21−7.16 (m, 1H), 2.02 (s,
δ (ppm) 158.2, 141.5, 139.9, 134.3, 133.2, 132.6, 130.1, 130.0, 129.2, 3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 138.9, 138.7, 136.9,
128.8, 128.3, 128.0, 127.8, 127.6, 126.4, 126.3, 125.6, 121.5, 120.9, 135.3, 132.8, 132.1, 131.4, 130.3, 130.2, 130.0, 129.4, 128.2, 128.0,
110.8, 55.8. MS (EI, 70 eV; m/z (relative intensity)) 392 ([M + 2], 128.0, 127.8, 126.6, 126.1, 125.6, 125.5,19.7. MS (EI, 70 eV; m/z
20), 391 ([M + 1], 25), 390 (100), 388 (53), 387 (20), 386 (20), 310 (relative intensity))376 ([M + 2], 20), 375 ([M + 1], 25), 374 (100),
(62), 295 (13), 282 (24), 203 (34), 202 (84), 77 (11). HRMS calcd 372 (53), 295 (11), 294 (31), 280 (11), 217 (44), 216 (45), 215 (89),
for C23H19OSe (ESI-TOF, [M + H]+) 391.0601, found 391.0610. 202 (67), 189 (12). HRMS calcd for C23H19Se (ESI-TOF, [M + H]+)
(4-Chlorophenyl)(1-phenylnaphthalen-2-yl)selane 2g. Title com- 375.0652, found 375.0663.
pound was isolated by column chromatography (hexane was eluent) as Phenyl(1-m-tolylnaphthalen-2-yl)selane 2o. Title compound was
a light yellow solid. Yield: 0.066 g (68%); mp 118.2−119.4 °C. 1H isolated by column chromatography (hexane was eluent) as a light
NMR (CDCl3, 400 MHz) δ (ppm) 7.82−7.77 (m, 1H), 7.69−7.63 yellow viscous oil. Yield: 0.066 g (72%). 1H NMR (CDCl3, 400 MHz)
(m, 1H), 7.52−7.45 (m, 3H), 7.45−7.40 (m, 2H), 7.39 (d, J = 8.6 Hz, δ (ppm) 7.79−7.74 (m, 1H), 7.64−7.59 (m, 1H), 7.53−7.48 (m, 2H),
2H), 7.37−7.30 (m, 3H), 7.28 (d, J = 8.7 Hz, 1H), 7.23 (d, J = 8.6 Hz, 7.46−7.36 (m, 3H), 7.35−7.23 (m, 6H), 7.17−7.12 (m, 2H), 2.41 (s,
2H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 140.2, 139.6, 136.0, 3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 140.0, 139.6, 138.0,
134.2, 133.1, 132.3, 130.3, 130.2, 129.6, 129.0, 128.5, 128.3, 128.3, 135.0, 133.2, 132.2, 130.9, 130.9, 130.8, 129.3, 128.5, 128.3, 128.3,
127.9, 126.6, 126.2, 125.7. MS (EI, 70 eV; m/z (relative intensity)) 128.0, 127.8, 127.2, 126.4, 126.2, 125.4, 21.5. MS (EI, 70 eV; m/z
394 (38), 314 (31), 278 (22), 207 (63), 202 (100), 176 (6), 138 (6), (relative intensity)) 376 ([M + 2] 20), 375 (24), 374 (100), 372 (52),
112 (5), 77 (33). HRMS calcd for C22H16ClSe (ESI-TOF, [M + H]+) 294 (61), 293 (31), 282 (35), 280 (29), 279 (54), 278 (36), 217 (17),
395.0106, found 395.0112. 216 (35), 215 (65), 202 (82), 189 (17), 163 (10), 77 (13). HRMS
(4-Fluorophenyl)(1-phenylnaphthalen-2-yl)selane 2h. Title com- calcd for C23H19Se (ESI-TOF, [M + H]+) 375.0652, found 375.0660.
pound was isolated by column chromatography (hexane was eluent) as Phenyl(1-p-tolylnaphthalen-2-yl)selane 2p. Title compound was
light yellow solid. Yield: 0.061 g (68%); mp 123.2−124.1 °C. 1H NMR isolated by column chromatography (hexane was eluent) as a light
(CDCl3, 400 MHz) δ (ppm) 7.81−7.75 (m, 1H), 7.68−7.61 (m, 1H), yellow viscous oil. Yield: 0.058 g (62%). 1H NMR (CDCl3, 400 MHz)
7.55−7.45 (m, 5H), 7.44−7.38 (m, 2H), 7.37−7.30 (m, 3 H), 7.25− δ (ppm) 7.80−7.74 (m, 1H), 7.64−7.59 (m, 1H), 7.54−7.48 (m, 2H),
7.19 (m, 1H), 6.98 (t, J = 8.8 Hz, 2H). 13C{1H} NMR (CDCl3, 100 7.47−7.43 (m, 1H), 7.42−7.36 (m, 1H), 7.35−7.22 (m, 9H), 2.46 (s,
MHz) δ (ppm) 163.0 (d, J = 248 Hz), 139.5, 137.4 (d, J = 8.0 Hz), 3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 139.8, 137.5, 136.7,
133.2, 132.2, 131.1, 130.2, 128.5, 128.2, 127.9, 127.7, 126.5, 126.1, 135.0, 133.3, 132.2, 131.1, 130.7, 130.1, 129.4, 129.2, 128.1, 128.0,
125.6, 125.0, 125.0, 116.6 (d, J = 21 Hz). MS (EI, 70 eV; m/z (relative 127.9, 127.9, 126.4, 126.2, 125.4, 24.4. MS (EI, 70 eV; m/z (relative
intensity)) 378 (34), 298 (29), 207 (100), 202 (89), 176 (5), 150 (4), intensity)) 374(100), 372 (51), 294 (67), 279 (53), 215 (66), 207
133 (26), 96 (42), 73 (53). HRMS calcd for C22H16FSe (ESI-TOF, (44), 202 (80), 189 (16), 77 (12). HRMS calcd for C23H19Se (ESI-
[M + H]+) 379.0401, found 379.0408. TOF, [M + H]+) 375.0652, found 375.0659.
(1-Phenylnaphthalen-2-yl)(3-(trifluoromethyl)phenyl)selane 2i. (1-(2-Methoxyphenyl)naphthalen-2-yl)(phenyl)selane 2q. Title
Title compound was isolated by column chromatography (hexane compound was isolated by column chromatography (eluent 1%
was eluent) as a light yellow oil. Yield: 0.061 g (57%). 1H NMR EtOAc in hexane) as a viscous dark orange oil. Yield: 0.072 g (74%).
(CDCl3, 400 MHz) δ (ppm) 7.86−7.77 (m, 1H), 7.75−7.65 (m, 2H), 1
H NMR (CDCl3, 400 MHz) δ (ppm) 7.78−7.74 (m, 1H), 7.65−7.61
7.62−7.54 (m, 1H), 7.53−7.40 (m, 6H), 7.40−7.25 (m, 5H). 13C{1H} (m, 1H), 7.49−7.35 (m, 6H), 7.34−7.28 (m, 1H), 7.24−7.16 (m, 4H),
NMR (CDCl3, 100 MHz) δ (ppm) 141.0, 139.5, 137.3, 133.1, 132.5, 7.10−6.99 (m, 2H), 3.64 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz)
132.3, 131.8 (q, J = 32.4 Hz), 130.5 (q, J = 3.7 Hz), 130.1, 129.6, δ (ppm) 157.4, 137.6, 134.2, 133.2, 132.4, 131.8, 131.4, 131.2, 129.5,
129.3, 128.8, 128.5, 128.4, 127.9, 126.6, 126.4, 126.0, 124.3 (q, J = 3.7 129.4, 129.2, 128.5, 128.1, 127.9, 127.4, 126.3, 126.2, 125.5, 120.6,

2720 DOI: 10.1021/acs.joc.7b00050

J. Org. Chem. 2017, 82, 2713−2723
The Journal of Organic Chemistry Article

111.3, 55.6. MS (EI, 70 eV; m/z (relative intensity)) 390 (17), 219 129.2, 128.4, 127.6, 127.6, 126.9, 126.1, 125.4, 124.1,19.3. MS (EI, 70
(17), 218 (100), 202 (16), 189 (51), 163 (18), 77 (8). HRMS calcd eV; m/z (relative intensity)) 374 (100), 294 (60), 279 (41), 215 (45),
for C23H19OSe (ESI-TOF, [M + H]+) 391.0601, found 391.0608. 202 (58). HRMS calcd for C23H19Se (ESI-TOF, M + H+) 375.0652,
(1-(4-Methoxyphenyl)naphthalen-2-yl)(phenyl)selane 2r. Title found 375.0659.
compound was isolated by column chromatography (eluent 1% (3,5-Dimethyl-1-phenylnaphthalen-2-yl)(phenyl)selane 2y. Title
EtOAc in hexane) as an orange solid. Yield: 0.071g (73%); mp 106.8− compound was isolated by column chromatography (hexane was
111 °C. 1H NMR (CDCl3, 400 MHz) δ (ppm) 7.79−7.75 (m, 1H), eluent) as a dark green solid. Yield: 0.063 g (65%); mp 149.1−153.2
7.64−7.60 (m, 1H), 7.54−7.50 (m, 2H), 7.48−7.44 (m, 1H), 7.43− °C. 1H NMR (CDCl3, 400 MHz) δ (ppm) 7.98−7.95 (m, 1H), 7.41−
7.38 (m, 1H), 7.36−7.33 (m, 1H), 7.32−7.22 (m, 6H), 7.06−7.02 (m, 7.35 (m, 3H), 7.34−7.30 (m, 1H), 7.26−7.14 (m, 4H), 7.12−7.05 (m,
2H), 3.89 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 159.3, 3H), 7.05−6.99 (m, 2H), 2.72 (s, 3H), 2.60 (s, 3H). 13C{1H} NMR
139.4, 135.1, 133.5, 132.2, 131.9, 131.6, 131.4, 130.6, 129.4, 128.0, (CDCl3, 100 MHz) δ (ppm) 147.4, 141.9, 139.2, 134.3, 133.4, 132.9,
127.9, 127.9, 126.4, 126.2, 125.4, 114.0, 55.3. MS (EI, 70 eV; m/z 132.0, 129.8, 129.0, 129.0, 127.8, 127.4, 127.1, 126.1, 125.5, 125.1,
(relative intensity)) 392 ([M + 2], 20), 391 ([M + 1], 25), 390 (100), 124.6, 24.8, 19.6. MS (EI, 70 eV; m/z (relative intensity)) 388 (100),
388 (53), 310 (62), 295 (13), 202 (18), 189 (82), 163 (14), 77 (12). 386 (53), 308 (44), 293 (33), 229 (22), 215 (84). HRMS calcd for
HRMS calcd for C23H19OSe (ESI-TOF, [M + H]+) 391.0601, found C24H21Se (ESI-TOF, M + H+) 389.0808, found 389.0817.
391.0613. (7-Methoxy-3-methyl-1-phenylnaphthalen-2-yl)(phenyl)selane
(1-(4-Chlorophenyl)naphthalen-2-yl)(phenyl)selane 2s. Title 2z. Title compound was isolated by column chromatography (eluent
compound was isolated by column chromatography (hexane was 1% EtOAc in hexane) as a light green solid. Yield: 0.067 g (67%); mp
eluent) as a light yellow viscous oil. Yield: 0.078 g (80%). 1H NMR 121.2−123.8 °C 1H NMR (CDCl3, 400 MHz) δ (ppm) 7.73−7.64 (m,
(CDCl3, 400 MHz) δ (ppm) 7.79 (d, J = 8.7 Hz, 1H), 7.65 (d, J = 8.7 2H), 7.41−7.31 (m, 3H), 7.22−7.10 (m, 3H), 7.10−6.97 (m, 5H),
Hz, 1H), 7.50−7.45 (m, 4H), 7.45−7.40 (m, 1H), 7.40−7.34 (m, 2H), 6.66 (d, J = 2.3 Hz, 1H), 3.61 (s, 3H), 2.52 (s, 3H). 13C{1H} NMR
7.33−7.24 (m, 6H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) (CDCl3, 100 MHz) δ (ppm) 157.2, 145.7, 141.7, 136.9, 134.4, 132.9,
138.6, 138.0, 134.8, 133.9, 133.0, 132.2, 131.6, 131.0, 130.4, 129.4, 129.7, 129.7, 129.4, 129.0, 128.9, 128.6, 128.0, 127.9, 127.1, 125.4,
128.5, 128.4, 128.0, 126.7, 125.8, 125.7. MS (EI, 70 eV; m/z (relative 119.0, 106.2, 55.0, 24.1. MS (EI, 70 eV; m/z (relative intensity)) 404
intensity)) 396 ([M + 2], 43), 394 (100), 392 (50), 316 (24), 314 (100), 402 (45), 324 (40), 231 (19), 202 (27), 188 (22). HRMS calcd
(62), 282 (33), 279 (62), 236 (22), 202 (100), 201 (40), 200 (50), 77 for C24H21OSe (ESI-TOF, M + H+) 405.0758, found 405.0752.
(13). HRMS calcd for C22H16ClSe (ESI-TOF, [M + H]+) 395.0106, (7-Chloro-3-methyl-1-phenylnaphthalen-2-yl)(phenyl)selane
found 395.0111. 2aa. Title compound was isolated by column chromatography
(1-(4-Fluorophenyl)naphthalen-2-yl)(phenyl)selane 2t. Title com- (hexane was eluent) as a light green solid. Yield: 0.045 g (44%); mp
pound was isolated by column chromatography (hexane was eluent) as 151.5−154.1 °C. 1H NMR (CDCl3, 400 MHz) δ (ppm) 7.75−7.68
a white solid. Yield: 0.044 g (47%); mp 105.4−108 °C. 1H NMR (m, 2H), 7.41−7.35 (m, 4H), 7.35−7.32 (m, 1H), 7.17−7.12 (m, 2H),
(CDCl3, 400 MHz) δ (ppm) 7.81−7.77 (m, 1H), 7.67−7.63 (m, 1H), 7.10−7.05 (m, 3H), 7.03−6.98 (m, 2H), 2.55 (s, 3H). 13C{1H} NMR
7.51−7.47 (m, 2H), 7.45−7.39 (m, 1H), 7.38−7.36 (m, 1H), 7.36− (CDCl3, 100 MHz) δ (ppm) 146.2, 140.8, 139.9, 134.0, 132.6, 132.1,
7.27 (m, 7H), 7.23−7.16 (m, 2H). 13C{1H} NMR (CDCl3, 100 MHz) 131.5, 131.0, 129.9, 129.4, 129.0, 128.7, 128.1, 127.5, 127.5, 126.3,
δ (ppm) 162.5 (d, J = 247 Hz),138.8, 135.5, 135.5 (d, J = 3.5 Hz) 125.8, 24.4. MS (EI, 70 eV; m/z (relative intensity))408 (96), 406
134.9, 133.3, 132.3, 132.0 (d, J = 8.1 Hz), 131.3, 130.5, 129.4, 128.4,
(49), 330 (15), 328 (37), 293 (29), 216 (44), 215 (100). HRMS calcd
128.4, 128.0, 126.6, 125.9, 125.6, 115.5 (d, J = 21 Hz). MS (EI, 70 eV;
for C23H18ClSe (ESI-TOF, M + H+) 409.0262, found 409.0271.
m/z (relative intensity)) 380 ([M + 1], 9)], 379 (11), 378 (51), 376
Butyl(1-phenylnaphthalen-2-yl)selane 2ab. Title compound was
(26), 298 (63), 297 (31), 220 (100), 77 (12). HRMS calcd for
isolated by column chromatography (hexane was eluent) as a light
C22H16FSe (ESI-TOF, [M + H]+) 379.0401,found 379.0410.
yellow viscous oil. Yield: 0.059 g (70%). 1H NMR (CDCl3, 400 MHz)
1,1′-Binaphthyl-2-yl(phenyl)selane 2u. Title compound was
isolated by column chromatography (hexane was eluent) as a yellow δ (ppm) 7.81 (d, J = 8.1 Hz, 1H), 7.76 (d, J = 8.7 Hz, 1H), 7.60 (d, J =
viscous oil. Yield: 0.058 g (57%). 1H NMR (CDCl3, 400 MHz) δ 8.7 Hz, 1H), 7.53−7.35 (m, 5H), 7.34−7.27 (m, 3H), 2.84 (t, J = 7.4
(ppm) 8.0−7.92 (m, 2H), 7.84−7.79 (m, 1H), 7.75−7.70 (m, 1H), Hz, 2H), 1.63 (quint, J = 7.4 Hz, 2H), 1.37 (sex, J = 7.4 Hz, 2H), 0.87
7.62−7.56 (m, 1H), 7.50−7.42 (m, 4H), 7.42−7.34 (m, 2H), 7.31− (t, J = 7.4 Hz, 3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 140.3,
7.19 (m, 6H), 7.18−7.12 (m, 1H). 13C{1H} NMR (CDCl3, 100 MHz) 140.0, 133.2, 132.0, 130.3, 129.5, 128.4, 127.9, 127.8, 127.6, 127.3,
δ (ppm) 137.8, 137.3, 135.0, 133.8, 133.7, 132.5, 132.3, 132.2, 130.5, 126.3, 126.0, 125.2, 31.9, 26.7, 23.0, 13.5. MS (EI, 70 eV; m/z (relative
129.3, 128.4, 128.4, 127.9, 126.6, 126.3, 126.3, 126.0, 125.9, 125.6, intensity)) 341 ([M + 1], 17), 340 (100), 338 (42), 284 (36), 204
125.5. MS (EI, 70 eV; m/z (relative intensity)) 410 (24), 253 (100), (100), 203 (58), 202 (69). HRMS calcd for C20H21Se (ESI-TOF, M +
252 (92), 250 (30), 126 (17), 77 (6). HRMS calcd for C26H19Se (ESI- H+) 341.0808, found 341.0813.
TOF, [M + H]+) 411.0652, found 411.0688. (1-Butylnaphthalen-2-yl)(phenyl)selane 2ac. Title compound was
1,2′-Binaphthyl-2-yl(phenyl)selane 2v. Title compound was isolated by column chromatography (hexane was eluent) as an orange
isolated by column chromatography (hexane was eluent) as a light oil. Yield: 0.063 g (74%). 1H NMR (CDCl3, 400 MHz) δ (ppm)
yellow solid. Yield: 0.053g (52%); mp 80.8−83.5 °C. 1H NMR 8.01−8.02 (m, 1H), 7.78−7.73 (m, 1H), 7.61−7.57 (m, 1H), 7.53−
(CDCl3, 400 MHz) δ (ppm) 7.98 (d, J = 8.4 Hz, 1H), 7.95−7.91 (m, 7.47 (m, 2H), 7.47−7.39 (m, 3H), 7.26−7.18 (m, 3H), 3.34 (t,J = 7.3
1H), 7.87−7.83 (m, 1H), 7.82−7.78 (m, 2H), 7.67 (d, J = 8.4 Hz, Hz, 2H), 1.65 (quint, J = 7.3 Hz, 2H), 1.51 (sex, J = 7.3 Hz, 2H), 0.98
1H), 7.56−7.45 (m, 5H), 7.45−7.38 (m, 2H), 7.35−7.23 (m, 5H). (t, J = 7.3 Hz, 3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm)140.8,
13
C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 139.7, 137.2, 135.0, 133.3, 132.8, 132.3, 131.9, 131.6, 131.4, 129.3, 129.2, 129.1, 128.6,
133.4, 133.3, 132.9, 132.3, 131.2, 130.6, 129.4, 129.4, 128.4, 128.3, 127.7, 127.1, 127.0, 126.4, 125.6, 124.4, 32.9, 32.4, 23.2, 14.0. MS (EI,
128.2, 128.1, 127.9, 127.9, 127.9, 126.5, 126.2, 125.6. MS (EI, 70 eV; 70 eV; m/z (relative intensity)) 342 ([M + 2], 70), 340 (71), 295
m/z (relative intensity)) 411[M + 1 (16)], 410 (59), 408 (32), 333 (23), 217 (70), 216 (100), 215 (62), 141 (53), 115 (18). HRMS calcd
(20), 330 (45), 329 (38), 253 (64), 252 (100), 250 (36), 126 (12), 77 for C20H21Se (ESI-TOF, M + H+) 341.0808, found 341.0814.
(9). HRMS calcd for C26H19Se (ESI-TOF, [M + H]+) 411.0652, found Methyl(1-phenylnaphthalen-2-yl)sulfane 2ad. Title compound
411.0673. was isolated by column chromatography (hexane was eluent) as a light
(4-Methyl-1-phenylnaphthalen-2-yl)(phenyl)selane 2x. Title com- yellow viscous oil. Yield: 0.035 g (56%). 1H NMR (CDCl3, 400 MHz)
pound was isolated by column chromatography (hexane was eluent) as δ (ppm) 7.82 (t, J = 9.5 Hz, 2H), 7.56−7.43 (m, 4H), 7.41−7.27 (m,
a light yellow viscous oil. Yield: 0.064 g (68%). 1H NMR (CDCl3, 400 5H), 2.42 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 138.6,
MHz) δ (ppm) 7.98−7.91 (m, 1H), 7.52−7.39 (m, 7H), 7.38−7.16 137.3, 134.8, 132.9, 131.3, 130.5, 128.5, 128.1, 127.82, 127.7, 126.5,
(m, 7H), 2.57 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 125.7, 125.0, 123.4, 16.3. MS (EI, 70 eV; m/z (relative intensity)) 251
140.0, 138.8, 134.6, 134.5, 133.3, 131.6, 131.0, 130.4, 130.1, 129.3, ([M + 1], 20), 250 (100), 235 (68), 234 (65), 202 (32), 117 (19).

2721 DOI: 10.1021/acs.joc.7b00050

J. Org. Chem. 2017, 82, 2713−2723
The Journal of Organic Chemistry Article

HRMS calcd for C17H15S (ESI-TOF, [M + H]+) 251.0894, found 3H), 7.33−7.24 (m, 5H), 7.04 (d, J = 8.9 Hz, 2H), 5.62 (s, 1H), 3.88
251.0902. (s, 3H), 2.30 (s, 1H). 13C{1H} NMR (CDCl3, 100 MHz) δ (ppm)
Phenyl(1-phenylnaphthalen-2-yl)sulfane 2ae. Title compound 159.2, 137.5, 136.3, 133.4, 133.1, 131.8, 131.7, 131.5, 129.7, 128.4,
was isolated by column chromatography (hexane was eluent) as a 128.4, 128.2, 127.9, 127.1, 126.1, 126.0, 124.4, 122.7, 113.9, 113.8,
yellow oil. Yield: 0.032 g (41%). 1H NMR (CDCl3, 400 MHz) δ 89.7, 86.6, 62.8, 55.3. MS (EI, 70 eV; m/z (relative intensity)) 364
(ppm) 7.83−7.79 (m, 1H), 7.72 (d, J = 8.7 Hz, 1H), 7.51−7.41 (m, (59), 349 (20), 315 (27), 262 (79), 261 (29), 202 (31), 189 (65), 102
5H), 7.38−7.31 (m, 4H), 7.30−7.26 (m, 2H), 7.26−7.20 (m, 3H). (100), 73 (16). HRMS calcd for C26H21O2 (ESI-TOF, [M + H]+),
13
C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 140.3, 138.7, 136.2, 365.1542 found 365.1549.
133.2, 132.9, 132.3, 131.7, 130.4, 129.1, 128.3, 128.3, 127.8, 127.6, 1-Phenyl-2-naphthaldehyde 6e. Title compound was isolated by
127.0, 126.5, 126.4, 125.8. MS (EI, 70 eV; m/z (relative intensity)) column chromatography (eluent 1% EtOAc in hexane) as a light
312 (100), 235 (23), 234 (37), 203 (48). HRMS calcd for C22H17S yellow solid. Yield: 0.03 g (52%); mp 98−101 °C. 1H NMR (CDCl3,
313.1051, found 313.1059. 400 MHz) δ (ppm) 9.89 (s, 1H), 8.06 (d, J = 8.7 Hz, 1H), 7.95−7.89
General Procedure for the Reaction of 2-Organoselenyl- (m, 2H), 7.68−7.57 (m, 2H), 7.56−7.49 (m, 3H), 7.48−7.37 (m, 3H).
naphthalenes with n-Butyllithium Followed by Different 13
C{1H} NMR (CDCl3, 100 MHz) δ (ppm) 192.6, 146.5, 136.1,
Electrophiles. To a two-necked round-bottomed flask, under 135.3, 132.5, 131.3, 131.0, 128.7, 128.3, 128.3, 128.2, 128.2, 127.7,
argon, containing a solution of 2 (0.5 mmol) in THF (5 mL) and 126.8, 122.2. MS (EI, 70 eV; m/z (relative intensity)) 234 ([M + 2],
hexane (5 mL) at room temperature, was added dropwise n-BuLi (0.55 100), 216 (26), 214 (50), 205 (49), 202 (41), 189 (14), 156 (26), 129
mmol, of a 2.5 M solution in hexane). The reaction mixture was stirred (36), 108 (33), 94 (20). HRMS calcd for C17H13O (ESI-TOF, [M +
for 15 min, and then was gradually added a solution of the appropriate H]+), 233.0966, found 233.0970.
electrophilic species (0.55 mmol) in THF (2 mL), at 0 °C. The
reaction mixture was allowed to stir at 25 °C for the time indicated in
Scheme 6. After this time, the mixture was diluted in ethyl acetate (20
mL) and washed with a saturated aqueous solution of NH4Cl (3 × 10
■
*
ASSOCIATED CONTENT
S Supporting Information

mL). The organic phase was separated, dried over MgSO4, and The Supporting Information is available free of charge on the
concentrated under vacuum. ACS Publications website at DOI: 10.1021/acs.joc.7b00050.
(1-(4-Methoxyphenyl)naphthalen-2-yl)(p-tolyl)methanol 6a. Text, figures, spectroscopic data for all new compounds,
Title compound was isolated by column chromatography (eluent 4% X-ray results (PDF)
EtOAc in hexane) as a yellow oil. Yield: 0.04 g (45%). 1H NMR
Crystal data (CCDC 1525289) (CIF)
(CDCl3, 400 MHz) δ (ppm) 7.87−7.78 (m, 2H), 7.65 (d, J = 8.6 Hz,
1H), 7.42 (d, J = 5.4 Hz, 2H), 7.37−7.17 (m, 3H), 7.17−6.90 (m,
7H), 5.82 (s, 1H), 3.86 (s, 3H), 2.28 (s, 3H). 13C{1H} NMR (CDCl3,
100 MHz) δ (ppm) 158.9, 140.9, 139.1, 138.9, 137.4, 136.7, 133.0,
■ AUTHOR INFORMATION
Corresponding Author
132.8, 131.8, 131.1, 130.3, 129.2, 128.8, 128.1, 127.8, 127.4, 126.9, *E-mail: [email protected].
126.4, 125.9, 125.7, 124.5, 113.8,72.6, 55.2, 21.0. MS (EI, 70 eV; m/z
(relative intensity)) 354 (60), 336 (100), 321 (30), 304 (22), 260 ORCID
(23), 245 (16), 201 (27), 118 (58), 104 (23). HRMS calcd for Gilson Zeni: 0000-0003-1290-6478
C25H23O2 (ESI-TOF, [M + H]+) 355.1698, found 355.1706. Notes
(4-Methoxyphenyl)(1-(4-methoxyphenyl)naphthalen-2-yl)-
The authors declare no competing financial interest.

■
methanol 6b. Title compound was isolated by column chromatog-
raphy (eluent 7% EtOAc in hexane) as light yellow oil. Yield: 0.089 g
(96%). 1H NMR (CDCl3, 400 MHz) δ (ppm) 7.86−7.79 (m, 2H), ACKNOWLEDGMENTS
7.69 (d, J = 8.6 Hz, 1H), 7.45−7.39 (m, 2H), 7.35−7.28 (m, 1H), We are grateful to FAPERGS, CAPES and CNPq for financial
7.28−7.20 (m, 1H), 7.09 (d, J = 8.4 Hz, 2H), 6.99 (ddd, J = 16.0, 8.4, support. CNPq and CAPES are also acknowledged for the
2.2 Hz, 2H), 6.91 (dd, J = 8.3, 2.5 Hz, 1H), 6.87−6.82 (m, 1H), 6.75 fellowships (A.M.S.R. and G.Z.).

■
(d, J = 8.8 Hz, 2H), 5.79 (s, 1H), 3.85 (s, 3H), 3.72 (s, 3H). 13C{1H}
NMR (CDCl3, 100 MHz) δ (ppm) 159.0, 158.7, 139.0, 137.4, 136.2,
133.1, 132.9, 131.9, 131.1, 130.4, 128.5, 128.0, 127.8, 127.8, 126.9,
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2722 DOI: 10.1021/acs.joc.7b00050

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2723 DOI: 10.1021/acs.joc.7b00050

J. Org. Chem. 2017, 82, 2713−2723