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organic chemistry DOI: 10.6023/cjoc201910029 Review and progress

Chinese Journal of Organic Chemistry REVIEW

Advances in Synthetic Methods of Benzofulvenes

Shi Chuanxinga,b Feng Chen Guob,c Chen Yali*,a Zhang Shusheng*,b,c Lin Guoqiangb

(aSchool of Science, Shanghai University Shanghai200444))

(bShanghai Institute of Organic Chemistry, Chinese Academy of Sciences Shanghai Key Laboratory of Organic Synthetic Chemistry for Natural Products200032)

Innovative
(cShanghai University of Traditional Chinese Medicine Chinese Medicine Research Institute Shanghai201203)

SummaryThe structure of benzofulvenes exists in many natural molecules and bioactive molecules, and these molecules are often used as important synthetic building blocks in the fields of materials science and

metal organic chemistry. A lot of research has been done on the synthesis of benzofulvenes , especially the rapid development in the past two decades, a series of efficient synthetic methods have been developed.

According to the different initiation mechanisms of key skeleton construction reactions, these methods can be roughly divided into five categories: thermally initiated or photocatalytic diradical mechanism Cyclization

reactions, transition metal-catalyzed tandem cyclization reactions, nucleophilic or electrophilic reagent attack-induced cyclization reactions, free radical-induced cyclization reactions, and acid-promoted cyclization

reactions. Research progress in the synthesis of phenylfulvenes in recent years.

Key wordsbenzofulvene; transition metal catalysis; diradical;C—Hbond activation; cyclization reaction

Recent Advancement in Benzofulvene Synthesis

Shi, Chuanxinga,b Feng, Chenguob,c Chen, Yali*,a Zhang, Shusheng*,b,c Lin, Guoqiangb
(aCollege of Sciences,Shanghai University,Shanghai 200444)
(bCAS Key Laboratory of Synthetic Chemistry of Natural Substances,Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences,Shanghai 200032)
(cInnovation Research Institute of Traditional Chinese Medicine,Shanghai University of Traditional
Chinese Medicine,Shanghai 201203)

AbstractBenzofulvenes were widely found in natural products and bioactive molecules, and also served as important
building blocks in material science and transition-metal chemistry. Great efforts have been devoted to the efficient
synthesis of these interesting molecules, and rapid in progress has two decades. According to the types of the initiation of
the reaction, these methods can roughly be classified into five categories: thermal or photochemical cycling of enyne-
allenes or enediynes, transition metal-catalyzed sequential cycling reaction, electrophilicini or attophilici ated nucleack
Radical initiated cycling and acid promoted cycling. This review describes the important synthetic methods of
benzofulvenes according to their reaction types.
Keywordsbenzofulvenes; transition metal catalysis; radical; C—H bond activation;

Fullene[1]It is a class of molecules with a cyclopentadiene skeleton with an exocyclic carbon-carbon

double bond (Figure 1).early, its specific5-methylene-1,3-Cyclopentadiene (1a).With the in-depth understanding

of non-benzene aromatic phenomena, a large number of molecules with structures similar to fulvene have been

discovered, and the concept of fulvene has been further expanded, which generally refers to the formation of a

conjugated ring containing an odd number of atoms and an extracyclic double bond. with cross-conjugation (

cross-conjugation)Molecules of the structure (1b).Due to the existence of resonance, the electrons of the double
picture1 Fulenes and their resonance structures
bond outside the ring and the π electrons of the conjugated system on the ring are partially transferred to satisfy
Figure 1 Fulvene and its resonance structure
the aromaticity of the ring structure unit in the molecule.

* Corresponding authors. E-mail: [email protected] ; [email protected] Received October

25, 2019; revised December 17, 2019; published online January 3, 2020.
Project supported by the National Natural Science Foundation of China (Nos. 21572253, 21772216), the Strategic Priority Research Program of the Chinese
Academy of Sciences (No. XDB 20020100), and the Key Research Program of Frontier Science (No. QYZDY6SSWSLH02 ).
National Natural Science Foundation of China (Nos. 221572253, 21772216), Chinese Academy of Sciences Strategic Leading Science and Technology Project (No. XDB 20020100), Chinese Academy of Sciences Frontier Science Key Research (No. QYZDY-

SSWSLH026)Funded projects.

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organic chemistry Review and progress

At the same time, due to the transfer of the π electrons from the double bond outside the ring to the The condensation reaction of indene with aldehydes or ketones under the action of base catalysis is the synthesis of benzene

ring or the transfer of the π electrons from the ring to the outer double bond (Fig.1),There is a large and the traditional method of fulvenes. First, indene8Under the action of base, the proton is lost and

dipole moment in the molecule[2],Exhibit unique physical and chemical properties. transformed into an indene anion9,Then attack the carbonyl of aldehyde/ketone, dehydrate to form

Benzofulvene2Benzofulene and its derivatives are very important compounds in the fulvene benzofulvene10(Scheme 1).The functional group compatibility of this method is limited, and it is

structure. Benzofulvene and its derivatives contain an indene skeleton, also known as1- difficult to apply to the synthesis of benzofulvenes with different substituent structures[11].

Methyleneindene. Indene is the basic skeleton of many drug molecules and natural products[3],It is

also an important precursor of many material molecules[4].Compared with the indene skeleton, the

benzofulvene skeleton contains an exocyclic double bond, which is easy to be functionalized.

Benzofulvene is not only some active biomolecules[5]and the core structure skeleton of natural

products, but also an important class of synthetic intermediates[6](picture

Schema1Traditional methods for the synthesis of benzofulvenes

2). 2009Year,Sarpongresearch group[6b]A case of synthesis of resveratrol dimeric resveratrol
Scheme 1Traditional method of benzofulvene synthesis
using a benzofulvene skeleton intermediate was reported. Two active natural products were

obtained through a series of reactions from methoxy-substituted phenylbenzofulvene Benzofulene and its derivatives are widely used, and their synthesis methods have

quadrangularin Aandparthenocissin A.The nonsteroidal anti-inflammatory drug sulindac (4) also been developed rapidly. According to the different initiation methods of key cyclization

and sulindac (5) core skeleton also contains fluorine-substituted benzofulvene structure[5b]. reactions, the main methods for constructing benzofulvene skeletons can be roughly divided

Benzofulvene has also been used in the research of polymer functional materials, such as into five categories: Catalytic or thermally initiated allene-enyne or enediyne cyclizations,

polymers with such novel structures6, Can be used in optoelectronic materials and has a transition metal-catalyzed tandem cyclizations, nucleophilic or electrophilic attack-induced

bright future[7].The properties of the polymer can be changed by changing the functional cyclizations, free radical-induced cyclizations, and Lewis Acid-promoted cyclization reactions.

group. Benzofulvene and its derivatives contain a cyclopentadiene skeleton, which can be This paper will summarize the synthesis methods of benzofulvenes according to the above

used to prepare post-metallocene catalysts[8](Postmetallocene catalysts),metal zirconium reaction classification.

complexes7,Applied to asymmetric olefin polymerization[9],Diels-Alderreaction etc.[10].

1Photo- or Thermally Initiated Allene-Enyne or Enediyne Cyclization

reaction

Oh
Oh BergmanRing aromatization and related reactions are very important reactions in

the fields of organic chemistry, medicinal chemistry and material chemistry[12].These

Oh Oh Oh Oh reactions use enediynes and enyne-alkenes as substrates and often undergo a diradical

intermediate[12]. BergmanThe ring aromatization reaction is also one of the decisive factors
HO
Oh HO for the high antitumor activity of enediyne antibiotics. The structure of enediyne antibiotics
Oh
contains a diendiyne conjugated macrocycle.BergmanThe reaction forms phenyl difree
Oh
3a 3b radical active intermediates, which directly destroy tumor cellsdnachain, eventually
HO
parthenocissin A (E) quadrangularin A (Z)
triggering tumor cell apoptosis.

COOH COOH BergmanThe cyclization reaction takes place in the enediyneC1-C6bit, while Myers-
f f SaitoCyclization reaction[13]Occurs in the enyne-alkeneC2-C7, these two types of reactions are
Me Me
intermediates undergoing diradicals, and finally form benzene rings (Scheme 2).From the

h h point of view of the reaction mechanism, the two substrates form fulvene

o
S 4 S 5
o o

Zr NMe2
Me2N
m no NMe2
6 7

Schema2Several modes of ring aromatization of enediyne and enyne-allene

picture2 Bioactive Molecules and Functional Materials Containing Benzofulvene Skeleton
substrates Scheme 2Cycloaromatization patterns of enediyne and
Figure 2 Bioactive molecules and materials containing ben-
enyneallene substrates
zofulvene moiety

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Chinese Journal of Organic Chemistry REVIEW

The possibility also exists.2001YearPeterwait[14]Careful theoretical calculations have been PeterIt is predicted that the energy barrier of the cyclization reaction with terminal electron-

carried out for such cyclization reactions. The results show that the above C1-C5Cyclization withdrawing group substitution is low, and the experiment has been verified. Therefore, the author

compared toC1-C6andC2-C7The cyclization reaction does require a higher reaction activation synthesized a substrate with a strong electron-withdrawing group at the end of the alkynyl group14,

energy, so it is easier to form a benzene ring. However, the existence of an aromatic ring Tried to synthesize benzofulvene under the condition of light, but failed, and got theC1-C5Cyclized

system and the application of a bulky terminal substituent can promote C1-C5Cyclization indene product15,16.Experiments have shown that only using light, by1,2-Synthesis of benzofulvenes

reaction. If the end of the enediyne contains an electron-withdrawing substituent, the from diethynylbenzene is relatively difficult.

energy required for the cyclization reaction can be further reduced. 2006YearSchmittelresearch group[18]A case of benzoenyne-alkene17,A method for

1995Year,Schmittelwait[15]Studying Benzoenyne-Allene Substrates 11ofC2-C6 generating benzofulvene derivatives by thermal initiation. They introduced a free radical

During the cyclization reaction, it was found that the enyne-alkene substrate with clock module into the molecular structure (Radical clock)Cyclopropane, the ring-opening

special substituents12exist50Occurs at ℃C2-C7routineMyers-Saito cyclization to form product of cyclopropane was obtained, demonstrating the free radical process of this

benzene ring, when the temperature rises to84℃, can occurC2-C6 reaction. This reaction is accompanied by by-products20andtwenty one, the reaction yield is

cyclization reaction, the benzofulvene-based products were obtained in moderate relatively low (Scheme 4a).

yields (Scheme 3a).Although raw12enyne11After a simple transformation same year,Pascalresearch group[19]A case of thermally induced1,2-The reaction of

However, using this method for synthesis, the substrate applicability is still relatively diphenylacetylene to construct benzofulvene (Scheme 4b),This reaction is similar to the

limited[16]. traditional method of using such substrates to construct benzofulvenes, and will occur C1-C6,

2002Year,Sergueiresearch group[17]A case of photocatalytic1, 2- C1-C5Two cyclization reactions (Scheme 2).Their research group also

Diethynylbenzene14ofC1-C5The cyclization reaction (Scheme 3b).because

Schema3Photo- or Thermally Initiated Allene-Enyne Cyclization to Build Benzofulvenes

Scheme 3Synthesis of benzofulvenes by photo/thermal cycling of enyne-allenes

Schema4Thermally Initiated Allene-Enyne Cyclization to Benzofulvenes

Scheme 4Synthesis of benzofulvenes by photo/thermal cycling of enyne-allenes

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organic chemistry Review and progress

Try the reaction. Since there will be by-productstwenty fourThe formation of , resulting in a Reaction, followed by alkyne insertion and cyclization is an effective method for the construction of

low yield, the separation yield was only19%.This method requires260The high temperature benzofulvenes.

of ℃ cannot be widely applied to the synthesis of benzofulvene substrates. This study did 2008Year,Shibatawait[twenty one]A case of carbonyl-directed iridium-catalyzedC—H

not conduct a wider investigation on the substrates, but it proved that the substrates of Activation reaction, developed with acetophenone30and diphenylacetylene 29as the

benzoenediynes can be thermally initiated, occurC1-C5cyclization reaction to construct substrate, [Ir(cod)2] BF4(5 mol%)as catalyst, orthoC—H bond activation to construct o-alkenyl

benzofulvenes. acetophenone fragments. When the iridium catalyst system was changed to [Ir(cod)2]OTf (5

2008Year,Schmittelresearch group[20]A case report of photocatalytic enyne-alkene25 mol%),The main products of cyclization are benzofulvene and indenol[twenty two],A series of

ofC2-C6cyclization reaction. Empirically they synthesized allenyl terminal carbonyl cyclized benzofulvene products (Eq. 1).However, for the substrates that can produce

substitution, alkynyl terminalTIPSsubstituted substrate25, By screening different solvents exocyclic configurations, the author did not conduct sufficient research, and only

and irradiation wavelengths, the benzoenyne-alkene25at a wavelength of300 nmThree investigated one substrate. Although a product with a single configuration was finally

products of benzofulvene were obtained under the irradiation of a light source. The type of obtained, the configuration was not determined. The research group also tried other types

substrate in this case has a great influence on the reaction. Several specific substrates can of The iridium complex cannot obtain the cyclized benzofulvene product, and this method

obtain the product of benzofulvene, and the highest separation yield can reach51% (Scheme needs to use chlorobenzene as the solvent and reflux for a long time to obtain the product.

5).This example of photocatalytic construction of benzofulvene developed by the research

group can obtain benzofulvene in a simple way.

TIPS
hv(300 nm)
no-Hexane/1,4-CHD
o
h 25
TIPS TIPS
TIPS Me
Me Me
+
+
o o o
26 27 28(two iosmers)

300 nm hv

Schema5Photoinitiated allene-enyne cyclization to construct benzofulvenes

2011YearGloriusresearch group[twenty three]A case of rhodium-catalyzedC—H Bond activation
Scheme 5Synthesis of benzofulvenes by photo cycling of
enyne-allenes to construct benzofulvene derivatives (Scheme 6).Under optimal conditions, with [RhCp*Cl2]2and

AgSbF6For the co-catalyst, there are equal amounts of substances at the same timeCu(OAc)2When
It is simple and convenient to construct benzofulvenes by photo- or thermally
present, up to99%The cyclization product was obtained in the separation yield of . By fine-tuning the
initiating alkenediynes and enynes-alkenes. Generally speaking, the cyclization
reaction conditions, changing the solvent and reaction temperature, benzofulvene or indenol (non-
conditions of allene-enynes are milder than those of diynes. However, these
dehydrative vs.alpha-route,beta-route).The study found that copper acetate is very important for this
methods inevitably lead toBergmanCyclization product (C1-C6)orMyers-Saito
reaction. According to the experimental phenomenon, the author speculates that copper releases
Cyclization product (C2-C7) and other by-products. In addition, the applicability of
rhodium catalyst species through transmetallation during the catalytic cycle, which promotes the
substrates and the construction of extracyclic double bonds in the reported related
progress of the catalytic cycle. The author also found that different substituents of the substrate will
methods still need to be further studied.
lead to the final The difference of the product, that is, the substituent will affect the final product. In

the non-dehydration reaction mode (non-dehydrative)in, whenR1For isopropyl, tert-butyl and other
2Transition metal-catalyzed tandem cyclization reactions

bulky hindered substituents,R2When it is an electron-withdrawing group, indenol is obtained.R1is a

In recent years, the application of transition metals in organic chemistry has achieved
methyl or hydrogen atom andR2When it is an electron-pushing group, the product of benzofulvene is
unprecedented development, making the efficient construction of carbon-carbon and carbon-
obtained (alpha-route). GloriusThe functional group tolerance of this method developed by et al. is
heteroatom bonds mature. This development also provides many new ways for the construction of
very good. Whether it is a strong electron-withdrawing or electron-donating substituent or a
benzofulvene frameworks. In Under the catalysis of transition metals, the tandem cyclization
substrate of a heterocyclic compound, the reaction can proceed, and the reaction can also be
reactions provide an efficient method for the construction of benzofulvenes.
controlled to stay in the indenol stage. But for the ring The configuration of the external double bond
Carbon-hydrogen bond activation is a research hotspot in transition metal catalysis in recent years.
cannot be effectively controlled by this method.
point.applyRh, Ru, Ir, Pd, CoCatalyzedC—Hbond activation trigger

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Chinese Journal of Organic Chemistry REVIEW

One, another disadvantage is that the reaction will inevitably produce indenol as a by-product. The authors

speculate that the reaction mechanism is similar to that of rhodium-catalyzedC—HThe mechanism of bond

activation to construct benzofulvenes is similar.2019Nian Tan Ze and Zhu Ganguo's research group achieved the

same reaction using cobalt catalysis[24b].

2015Year, Hua Ruimao research group[25]Diphenylacetylene 45A class of

palladium-catalyzedC—Hbond activation to construct phenylfulvenes46Methods(

Scheme 8).The use of new substrates effectively avoided the formation of indenol by-

products. Finally, diphenylacetylene was catalyzed by palladium acetate in N,NA

series of phenyl-substituted benzofulvene compounds were obtained by adding

lithium bromide, cesium pivalate and other additives to dimethylacetamide in

moderate to high yields.

R R

Pd(OAc)2(5 ~ 10mol%)
LiBr (1.0 equiv.)
HOPiv (1.5 equiv.)
NaOAc (1.0 equiv.) R
R
Schema6 Rhodium-catalyzedC—HBond Activation to Build Benzofulvenes DMAc, 80 ~ 100o C
Scheme 6 Rhodium catalyzed synthesis of benzofulvenes 11 examples
39% ~ 81% yields
2012, using similar reaction substrates,Jeganmohanresearch group[24a]reported a R 46 R
45
class of inexpensive ruthenium-catalyzedC—HA method for the construction of
Ph Ph
benzofulvenes by bond activation. Reaction and rhodium-catalyzedC—HActivation similar, Pd(OAc)2
using similar substrates41exist[RuCl2(p-cymene)],Cu(OAc)2•H2O (25 mol%)Under the action,
Ph HOPiv
h
indenol products are formed43(Scheme 7).Other conditions remain unchanged, theAgSbF6 Pd(OPiv)X
m/z: 356Ph 47
usage increased to20 mol%,Get benzofulvene products44.However, the reaction did not
52
make progress in the configuration of the exocyclic double bond, which is one of the
(a)orthoCH
shortcomings of the acetophenone-based substrates for the construction of benzofulvenes.
(d) proton exchange palladtion
HX
(e) reductive
o
[RuCl2(p-cymene)]2(2 mol%) elimination Ph Ph
AgSbF6, Cu(OAc)2•H2O (25 mol%) OPiv
R1
+R2 R3
DCE, 10 hours Ph
41 42 Pd(OPiv) Ph
21 examples Pd(OPiv)
73% ~ 93% yields 48
51Ph
Ph
R2 R2 determined by GC-MS

R3 or R3 (a) 50Ph
(b) intermolecular
Oh inertion
R1 (c) intramolecular
43 R1 44 Ph
insertion
Ph
o Cp*Co(CO)I2(10 mol%) Pd(OPiv)
AgSbF6(25 mol%) Ph
KOAc (20 mol%) Ph 47
R1 +R2
R3 Ph
42 DCE, 130oC, 24 h
41 49
29 examples
42% ~ 92% yields
Schema8 palladium catalyzedC—HBond Activation to Build Benzofulvenes
R1
Scheme 8 Palladium catalyzed synthesis of benzofulvenes via
R3 (b) C—H activation

R2 2019Year, Zhuang Shiqing's research group[26]A similar reaction was reported in which a
44
benzofulvene framework was also constructed from two molecules of diaryleacetylene (Eq. 2).
Schema7 Ruthenium-catalyzedC—HBond Activation to Build Benzofulvenes
Apart fromC—HVarious reaction types catalyzed by transition
Scheme 7 Synthesis of benzofulvenes by ruthenium catalyzed
C—H bond activation metals can trigger corresponding reactions.

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organic chemistry Review and progress

1996Year,Dykerwait[27]A case of halogenated1,1-Diphenyl- 2-Vinyl bromide (56) as the

substrate, domino'sHeckThe method of reaction construction benzofulvene (Scheme 9),The

reaction first undergoes intermolecularHeckreaction, intramolecularHeckReaction to build

benzofullenes. The author did not investigate the functional groups of the substrates, but

only expanded the substrates from the perspective of building macrocycles and synthesized

a series of benzofulenocyclic structures.

x
PD
+ Pd0

- HX
X = Br, I
57
56
+1
a

-HPdX wxya

59 58
Schema10 Asymmetric Cumulative Alkene Domino Reaction to Build Benzofulvenes

Schema9 Palladium Catalyzed DominoesHeckreaction

Scheme 10 Synthesis of benzofulvenes via domino reaction
with unsymmetrically substituted cumulene
Scheme 9Palladium catalyzed domino heck reaction

2006Year,Toberesearch group[30]L ', hvbnm; N1,6-Substrates of Disubstituted

2004Year,Singerresearch group[28]developed with2-Halogenated phenylacetonitrile60 With

Alkyne Diene Structures66,Construction of bridged benzofulvene derivatives under

ethyl ethoxy acrylate (61) reaction to construct cyano-substituted benzofulvene derivatives62

the catalysis of palladium67(Eq. 4).This rigid large conjugated bridged benzofulvene

Methods(Eq. 3).The author synthesized benzofulvene only as a key intermediate in the synthesis of

skeleton molecule is a class of excellent second-order nonlinear optical

other compounds, and did not conduct an in-depth investigation on the functional group

chromophores (Second Order Nonlinear Optical Chromophores)Compounds can be

compatibility of the substrates, but only investigated a few simple substrates. This method

used as core raw materials for some advanced optical devices.

synthesized cyano-substituted benzene The benzofulvene derivatives are beneficial to the

2009Year, Wang Jianbo's research group[31]A case of gold-catalyzed ring expansion of unsaturated
functionalization of the benzofulvene skeleton, and the chlorinated substrates are also suitable for

three-membered rings to construct benzofulvenes (Scheme 11). unsaturated substrate68The carbon-carbon

this reaction.

double bond of the carbon-carbon double bond coordinates with the gold ion, and then the three-membered
2006Year,Kanresearch group[29]A case of palladium-catalyzed multistep Heck

ring opens to form a gold carbene71,The ensuing carbene insertion reaction gives 72,Then, under the action of
reaction, a method for constructing benzofulvenes from accumulated trienes (Scheme 10).

alkali, one molecule of acetic acid is eliminated to obtain the product69.This method studies the synthesis of
Although in63In the presence of conjugated aldehyde groups, the arylpalladium species will

simple benzofulvene derivatives, and does not involve the investigation of exocyclic double bonds.
still be inserted into theC3-C4between, forming six-membered ring palladium species64, Final

reductive elimination yields benzofulvene derivatives65.

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Chinese Journal of Organic Chemistry REVIEW

2010In 2010, the research group subsequently reported two cases of synthesis of
r1
Pd(OAc)2(20 mol%) A Ar1
Ar1 PPh3(40mol%)
benzofulvenes from gem-dibromosubstituted alkenylbenzenes. Using75[33a]and77[33b]
Br + (4)
Bu4NBr as the substrate. Under the catalysis of palladium acetate, with triphenylphosphine as the
Ar2
K2CO3, DMF Ar2
Ar2 ligand, adding base, intramolecularHeckreaction, followed by aryl boronic acidsuzuki

66 Z-67 E.-67 Reaction to construct benzofulvene derivatives (Scheme 12a).This method has mild reaction
S
conditions, moderately high yields, etc., and avoids the situation where the extracyclic

double bond produces a mixture.

S
S S
85% 89% 38%
Z/E.=75/25 Z/E.=89/11 Z/E.=77/23
S

S S

49% 87% Schema12 palladium catalysisSuzuki/HeckCascade reactions to construct

Z/E.=83/17 Z/E.=100/0
Scheme 12 benzofulvenes Pd-catalyzed tandem Suzuki/Heck reaction of 1-
(2,2-dibromovinyl)-2-alkenylbenzenes

same year,Lautensresearch group[34]Utilize similar bromodienyl substrates77byPD2

dba3as the source of palladium, cesium carbonate as the base, and trifurylphosphine as the

ligand, in60Derivatives of benzofulvene can be obtained in a mixed solvent of dioxane and

water at ℃78(Scheme 12b).

2010Year,Kimresearch group[35]byBaylis-HillmanThe addition product is the

raw material and undergoes a one-step reaction to obtain the product79,then pass

Barbierresponse to get80,intramolecularHeckReactive elimination of benzofulvene

mixtures to construct cis-trans isomers81(Scheme 13).

Schema11Gold-catalyzed three-membered cycloisomerization to construct benzofulvenes

Scheme 11Au-catalyzed isomerization of cyclopropenes to build

benzofulvene derivatives

2009Year, Wu Jie's research group[32]A palladium acetate-catalyzed cascade reaction for the

construction of chlorobenzofulvenes74(Eq. 5).The author believes that the reaction is initiated by divalent

palladium, which coordinates with the alkynyl group, and the chloride ion attacksCCTriple bond, followed by

double bond insertion reaction, the product is formed after reduction elimination74and zero-valent palladium

species. Zero-valent palladium regenerates divalent palladium in the oxidation of copper ions, and continues to

participate in the next round of catalytic cycle. This method usesE.conformation of the substrate, theHeckAfter

the insertion of the reaction double bond, the cis-elimination will not produce the situation that the extracyclic

double bond is a mixture. This method provides a reference for the synthesis of benzofulvene derivatives with a
Schema13 Depend onBaylis-HillmanAddition products to build
single configuration of the extracyclic double bond. Scheme 13 benzofulvenes Building benzofulvene derivatives from Baylis-
Hillman adduct

2013year, the research group[36]Improved the above work, using trans-conjugated diene structure

substrate82,By controlling the different bases (triethylamine and cesium carbonate), the basic control of the

configuration of the extracyclic double bond of several substrates with different functional groups was achieved,

and different main products were obtained respectively.81.

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organic chemistry Review and progress

2012Year, Zhang Xingguo's research group[37a]A palladium-catalyzed synthesis of

Oh Ar
benzofulvene derivatives was reported (Scheme 14).This work directly uses the chlorinated R1Ar
R2 (PhO)3PAuCl
R1
substrate84As substrate, oxidative addition to palladium, alkyne insertion followed by R3 AgNTf2(5 mol%) OH+
R2
boronic acidSuzuki-MiyauraCoupling reaction to obtain trifluoromethylated benzofulvene. R3
N 12 examples
This reaction provides a new method for the construction of benzofulne and the synthesis of 87 up to 84% yields N
trifluoromethylated benzofulvene through a series of cyclization-coupling reactions.2018 88
Ar
year they[37b]This reaction was further extended to synthesize indole- or pyrrole-substituted
R1
(6)
benzofulvenes directly using organic amines as coupling fragments. R2
R3
R2 ArB(OH)2R1 N
CF3
Cl [Pd]/L1
R1 89
K2CO3
CF3 R2
19 examples Ar
84 up to 98% yields
85

PCy2
iPR iPR

iPR
L1

R3
R2 N R1 CF3
h
[Pd]/L
Cl N
R1 R2
t-BuONa
CF3
84 19 examples
up to 76% yields 86 Dialkynylbenzene as a substrate, with5 mol% Ph3wxya2As a catalyst, benzofulvene
R3
derivatives of oxa six-membered rings were obtained in dichloromethane solution.

PCy2
2015Year,Hamzewait[41]A one-pot method for the tandem synthesis of benzofulvenes was reported. The

method uses o-alkynyl hydrazones93As the substrate, through the regulation of the ligand, the coupling and

L2 ring-forming reaction of the hydrazone and the halogenated hydrocarbon can be realized sequentially (Eq. 9).

Schema14 Palladium-Catalyzed Tandem Cyclization-Coupling Reaction to Construct Benzofulvenes

Scheme 14 Synthesis of 2-CF3-Benzofulvenes via Pd-catalyzed

tandem carbocyclization-coupling reactions

2012Year,Sanzresearch group[38a]A gold-catalyzed cyclization tandem reaction method was

developed to construct benzofulvene derivatives. This method also needs to undergo gold cation

species, and after cyclization, an exocyclic double bond is obtained by elimination reaction (Eq. 6),

Finally, a higher yield was obtained (E.)-89main product.2015 year they[38b]The conversion of this

reaction was achieved using p-toluenesulfonic acid catalysis without the need for metal catalysts. 2016Year,Leeresearch group[42]A method for the construction of benzofulvenes by rhodium-

catalyzed denitrogenation and cyclization of triazoles was reported (Scheme 15).Triazole95 In the

2014Year, Chen Zhiyuan's research group[39]A platinum-catalyzed cyclization cascade reaction presence of divalent rhodium, one molecule of nitrogen gas is removed, and the generated rhodium-

was developed to construct benzofulvene derivatives (Eq. 7).The authors believe that the reaction first carbene intermediate electrophilically attacks the benzene ring, and after the metal rhodium leaves, it

undergoes the acyl[3,3]-The rearrangement reaction generates an allene intermediate, which is then rearranges to obtain benzofulvene96.Triazoles can be synthesized from alkynes and azides via copper

catalyzed by metal platinum for ring closure, and finally [1,5]-The acyl group migrates to obtain an catalysisClickThe response is obtained.94and sulfonyl azide in the catalystCuTCand Rh2(S-DOSP)4

exocyclic double bond asZproduct of configuration. Under the catalysis of , a one-pot synthesis of benzofulvenes is possible. This work employs a series of

2013Year, Yao Zhujun Research Group[40]A case of gold-catalyzed benzofulvene- novelly designed substrates, and finally obtains a series of amino-functionalized benzofulvene

derived synthesis was also reported (Eq. 8).They designed a carboxylated derivatives.

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Chinese Journal of Organic Chemistry REVIEW

x o
x GF o
o N3 CuTC R2 Pd(OAc)2 o
GF N Oh
+S Cu(OAc)2•H2o
R o o N N +
S tAmOH, 85oC
R1 R3 R1
94 95 R o R3
o 12 hours

101 R2
98 102
Rh2(S-DOSP)4 GF x
Cu(OAc)2 Pd(OAc)2
(1 mol%)
2 AcOH
DCE, 80oC, 12 h o
16 examples HN o
up to 75% yields o o
OS o o PD
96
R
o
OC Pd
o
Schema15 One-pot Synthesis of Aminobenzofulvenes

Scheme 15 One-pot synthesis of amino substituted benzoful- Ph Ph

Ph Ph
venes
Ph
Ph
2018Year, Zhang Yanghui research group[43]iodobenzene97, alkyne98and dibromomethane99A three-
o o
o o
component cascade reaction to prepare benzofulvenes under palladium catalysis (Eq. 10).The authors believe

o
that the reaction has undergone cyclopalladium intermediates, iodobenzene and alkynes form cyclopalladium

PD PD
species with metal palladium, and then couple with dibromomethane to obtain indene, which is condensed with Ph o Ph
another molecule of dibromomethane under alkaline conditions to obtain benzofuran alkene.
Ph Ph

Schema16 Palladium-catalyzed synthesis of benzofulvenes containing phthalide fragments

Scheme 16 Synthesis of phthalide-fused benzofulvenes

thing103The method (Eq. 12).The method has mild

reaction conditions and a wide range of substrates.

2019Year, Wu Xiaofeng Project[44]The group reported a palladium-catalyzed four-

component reaction to construct benzofulvenes (Eq. 11).Using simple and readily available

starting materials, this method provides polysubstituted benzofulvenes in moderate yields

in one step.

Construction of cyclopentadiene rings through different strategies and synthetic building blocks is the benzo

The main synthesis methods of fulvenes.2019YearBlondwait[47]reported a completely different

strategy for the synthesis of benzofulvenes by directly constructing benzene rings (Eq. 13).Using pre-

organized triynes as substrates in [Rh(CO)2]2Under the catalysis of alkynes, alkynes are aromatized to

construct benzene rings to obtain products with polycyclic skeletons. The reaction will also generate

by-products of cycloheptatrienone skeletons. This method can synthesize multi-substituted

asymmetric polycyclic benzofulvenes.

same yearGogoiwait[45]A palladium-catalyzedCHActivation/alkyne insertion decarbonylation

reaction (Scheme 16).Using this method, benzofulvenes containing phthalide fragments can be

synthesized conveniently. The reaction uses hydroxynaphthoquinone101As substrate, with alkynes

under the catalysis of palladium acetate, throughCHActivation, alkyne insertion, rearrangement

decarbonylation, reductive elimination to give the product102.The palladium regenerates divalent

palladium under the oxidation of copper acetate to realize the catalytic cycle.

Hashmiresearch group[46]A double-gold-catalyzed non-conjugated diyne substrate is reported

Chin. J. Org. Chem.2020,40, 817~830 © 2020 Chinese Chemical Society & SIOC, CAS http://sioc-journal.cn/ 825
organic chemistry Review and progress

3Cyclization reactions initiated by attack by electrophiles or nucleophiles

Use electrophile or nucleophile to attack the benzo that initiates the cyclization reaction

The synthesis of fulvenes has been reported for a long time.1969YearReichardt

research group[48]studied simple electrophiles such as hydrogen bromide, water,

iodine or bromine and other benzoendiyne substrates108Impact(Scheme 17).Two

isomers are produced when hydrogen bromide gas or hydrogen bromide in acetic 2014Year, Chen Zhiyuan's research group[51]reported a caseBiCl3or TOHFacilitated

acid solution is added106, 113,Adding bromine or iodine will generate dibromo or Cascade Reaction Synthesis of Trifluoromethylthio-Substituted Benzofulvenes (Eq. 16).useN-(

diiodo benzofulvene derivatives111,Adding bromine and methanol gives Trifluoromethylthio)aniline provides electrophilic trifluoromethylsulfide ions, which can

bromoindene product114. promote the electrophilic ring closure of diynes and facilitate the nucleophilic reaction of

chloride ions or p-toluenesulfonate ions.

o
Ph Ph
Br

Ph
Ph
Br
114 Br
113
Zn
+
Br2 CH3Oh
Br Ph o
Ph Ph

HBr h3o
Ph Ph
2014Year,Martinelliwait[52]first synthesized by two simple reactions1,2-

109 108 Ph 115 Diarylalkynylbenzene, and then use iodine to promote cyclization to construct

BuLi Br2(I2) iodobenzofulvene, and through coupling reaction, the conjugated molecule with multi-

substituted benzofulvene skeleton is finally obtained (Eq. 17).

(I)Br Ph
Ph Ph Br(I)

Ph Ph Ph

cis-110 Br(I) Br(I)

111 112

Schema17 Introduction of electrophile to promote cyclization reaction to construct benzofulvene

Scheme 17 Enediyne cycling promoted by electrophiles to

build benzofulvene derivatives
4 Free Radical Initiated Cyclization Reaction

2003Year,Schreinerresearch group[49a]A method for the construction of

2001Year,Schreinerresearch group[53]Using an enediyne substituted with a carbonyl
polyphenyl substituted benzofulvenes was reported (Eq. 14).The method uses
group as a substrate, theTEMPOAs an initiator, reflux in toluene gave5-Exo-Digtype ring-
enynes 116,Reaction with elemental bromine gave polyaryl-substituted
closing intermediate, and the fulvene product was obtained after hydrogen abstraction.
bromobenzofulvenes. 2017YearSanzwait[49b]Using the same strategy, useNISAs an
However, when this method was used for the synthesis of benzofulvene derivatives, only5-
electrophile, iodobenzofulvene was obtained.
Exo-Digtype ring-closing reaction, to getBergmanCyclization product, no benzofulvene was

formed.

2004Year,Alabuginresearch group[54]Tried to synthesize benzofulvenes by free

radical cyclization. They used traditional enediynes as substrates, inAIBNInitiated by using

tributyltin hydrogen as a free radical source, tin-substituted benzofulvene derivatives were

synthesized for the first time, and phenyl-substituted benzofulvenes were obtained in

moderate yields after acidification (Scheme 18).This method is different from BergmanThe

diradical mechanism of cyclization is a free radical chain reaction initiated by an initiator.

2007Year, Huang Xian's research group[50]The aluminum chloride-promoted tandem
Moreover, this method cannot effectively control the configuration of the double bond
ring-opening/cyclization reaction of acid chlorides and alkylene cyclopropanes to construct
outside the ring, and the result isZ/E.A mixture of configurations.
benzofulvenes was reported (Eq. 15).This method can conveniently synthesize functionalized
Subsequently,Alabuginresearch group[55]The origin of the hydrogen atoms in the exocyclic olefins in the
benzofulvenes under mild conditions, and generates highly selectiveZ-configured exocyclic
benzofulvene products was investigated (Scheme 19).Through the deuteration experiment, it was found that the
double bond.
hydrogen atom was derived from tert-butyltin hydrogen, which confirmed that the reaction was

826 http://sioc-journal.cn/ © 2020 Chinese Chemical Society & SIOC, CAS Chin. J. Org. Chem.2020,40, 817~830
Chinese Journal of Organic Chemistry REVIEW

·
·

o40etc., can catalyze the reaction.

Schema18Free radical-promoted cyclization to construct benzofulvenes

Scheme 18Radical induced synthesis of benzofulvenes 2014Year,Coelhoresearch group[58]reported a casep-TsOHCatalyzed cyclization reaction to

construct the method of benzofulvene (Scheme 20).The method uses tetraaryl-2-Butyne-1,4-diol137as

the substrate, in a catalytic amount ofp-TsOHUnder the action of Naphthol, it reacts with naphthol to

rapidly generate multi-substituted benzofulvenes 138.substrate137It can be obtained by reacting

diphenyl ketone with ethynyllithium, and then undergoes Friedel-Crafts alkylation reaction with

naphthol under the catalysis of an acid, and then isomerizes to an allene intermediate, and then

undergoes a cyclization reaction to obtain the final benzene

Oh Ar
Ar OR
Ar
Ar
A
Oh
h R
R 137
Ar
Ar
Ph
HO 138
Ph Ph Ph
Schema19 Deuterium experiment C h+ C Ph
Ph C C Ph
Scheme 19 Deuterium-labeling experiments C -H2o Ph C
Ph Ph
Oh Oh PhOH
Free radical chain reaction. This study provides a useful reference for the Ph
Oh Oh
synthesis of stable isotope-labeled benzofulvenes.

2019Nian , Jiang Bo et al[56]A free radical-initiated reaction to construct h+

Ph Ph-H2o
benzofulvenes was reported (Eq. 18).they useDABCO•(SO2)2complexes as initiators,
C
C Ph Ph
with diazonium salts133One-electron transfer occurs, sulfur dioxide intercalates to Ph C Ph
Ph Oh
generate sulfonyl radicals and releases nitrogen gas, and sulfonyl radicals attack Ph Oh
Oh Oh Oh
another alkyne molecule134,Then a series of free radical cyclization reactions occurs

to generate polycyclic sulfone compounds with benzofulvene skeletons135.

Ph Ph
Ph
5Acid- or base-promoted cyclization reactions C C Ph
Ph Ph Ph C
Ph
Ph
2009Year,Gandonresearch group[57]reported an acid-catalyzed synthesis of
h

benzofulvenes (Eq. 19).This method uses a class containingalphaSubstrates for

-hydroxyalkene backbone136,Occurs under the action of acidNazarov-Type Schema20 Acid Catalyzed Construction of Polyaryl Substituted Benzofulvene Derivatives

cyclization to construct benzofulvene. It was found that Lewis acid and Bronsted Scheme 20 Acid catalyzed synthesis of multi-substituted ben-
zofulvenes
acid, such asZnCl2, Zn(OTf)2, Cu(OTf)2, AgOTf, TfOH, H3PMo12-

Chin. J. Org. Chem.2020,40, 817~830 © 2020 Chinese Chemical Society & SIOC, CAS http://sioc-journal.cn/ 827
organic chemistry Review and progress

and fulvene products. The characteristics of this method are that the substrate is easy to prepare, the reaction is The reduction of ions gave this method a new vitality. Using enediyne and enyne-alkene

simple, and highly substituted polyaryl benzofulvenes can be obtained. substrates, in the early stage, electrophiles were mainly introduced to accelerate the

2014Year,Matsubararesearch group[59]Lithium-catalyzed Nazarov-Type cyclization reaction, and later photocatalytic or Thermally initiated cyclization reaction.

Cyclization builds the synthetic method of benzofulvene (Eq. 20), Lithium catalysis is However, the use of such substrates for cyclization reactions inevitably producesC1-C6

more environmentally friendly than transition metal catalyzed reactions. cyclized benzene ring products, because the energy required for this type of cyclization is

low.

twenty oneCenturies later, with various coupling reactions (Heck, Suzuki)and C—H

Bond activation is applied to the synthesis of benzofulvene skeletons, and the substrates for

benzofulvene synthesis become rich and diverse. Benzoketone substrates can be catalyzed

by transition metalsC—HHowever, this method is always accompanied by the formation of

indenol by-products. The substrates of gem-dibromoenynes can be directly synthesized by

2019YearInglesonwait[60]reported the synthesis of boronic acid derivatives of intramolecular coupling reactions To construct benzofulene products, this kind of method

benzofulvenes by borylation of diacetylenylbenzene (Scheme 21).Lewis acidBCl3Initiates the has mild reaction conditions, which has improved the situation that the previous synthesis of

cyclization of alkynes and at the same time serves as a boron source. When zwitterions are benzofulvene skeletons required severe conditions. However, the scope of substrate

generated, one reaction pathway is to grab aClions to generate chlorobenzofulvene boronic practicability needs further study.

acid, and another reaction pathway is to attack the benzene ring to generate Recently, the methods for synthesizing benzofulene skeletons have become more abundant. By

dibenzopentalene. Use positively chargedCl2B (lutidine)+, the reaction is more inclined to designing appropriate cascade reactions, simple substrates can be used to synthesize benzofulvene products

form dibenzopentalene143,while adding (NBu4)BCl4After that, you can increase the with complex structures in one pot. In terms of substrates, the application of both polyene substrates In addition

benzofulvene142proportion. to the synthesis of benzofulvene, there are accumulated olefin-type substrates to synthesize benzofulne

skeletons, and saturated three-membered rings can also be catalyzed by gold to construct benzofulvene.

R
R
6.2outlook
BCl3
Although many methods have been developed for the synthesis of benzofulvenes, there are
R
still problems to be solved. For example, the configuration control of the extracyclic double bond has
BCl3
not been solved well. Although for some special substrates, it can be achieved Effective control, but
141 R
not universal. It is necessary to develop a method that can control the configuration of the double
R
R bond outside the ring of benzofulvene and is applicable to a wide range of substrates. In addition, the

Cl
substrates for synthesizing benzofulvenes basically contain Carbon-carbon triple bonds or allenes,
R
+
there are few studies on substrates containing only carbon-carbon double bonds, and this aspect is
R
expected to become a trend in the synthesis of benzofulvenes in the future.

BPin
BPin References
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