Enantioselective Formal (3+3) Cycloadditions of Ketones and Cyclic 1-Azadienes by Cascade Enamine-Enamine Catalysis
Enantioselective Formal (3+3) Cycloadditions of Ketones and Cyclic 1-Azadienes by Cascade Enamine-Enamine Catalysis
Enantioselective Formal (3+3) Cycloadditions of Ketones and Cyclic 1-Azadienes by Cascade Enamine-Enamine Catalysis
Abstract: An asymmetric formal [3+3] cycloaddition process reaction to afford spirocyclic architectures in excellent dia-
with diversely structured aliphatic ketones and electron-defi- stereo- and enantioselectivity. Importantly, high regioselec-
cient cyclic 1-azadienes was developed by cascade enam- tivity was realized for a number of unsymmetrical aliphatic
ine–enamine catalysis of a cinchona-based primary amine. ketone substrates.
This sequence involved a domino Michael addition–Mannich
Chem. Eur. J. 2015, 21, 1 – 7 1 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim & &
amino-9-deoxyepiquinine (1 a) and salicylic acid A1 at room mized the reaction with amine 1 c, and a good ee value could
temperature.[11] To our delight, the desired formal [3+3] cyclo- be obtained at lower temperature, though a modest yield was
addition reaction occurred smoothly to give spirocyclic prod- given even after a longer time (entry 16).
uct 4 a as a single diastereomer in various solvents (Table 1, en- With the optimized catalytic conditions in hand, the sub-
tries 1–6), and excellent results were obtained in THF in consid- strate scope and limitations of the formal [3+3] cycloaddition
reaction were explored (Table 2). At first, an array of aliphatic
& & Chem. Eur. J. 2015, 21, 1 – 7 www.chemeurj.org 2 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2015, 21, 1 – 7 www.chemeurj.org 3 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim & &
(1’S,5’S)-5’-Phenyl-2H-spiro(benzo[d]isothiazole-3,1’-cyclo-
hexan)-3’-one 1,1-dioxide (4 a)
Obtained as a white solid in 85 % yield after flash chromatography
and the enantiomeric excess was determined to be 97 % by HPLC
analysis on Chiralpak OD-H column (40 % 2-propanol/n-hexane,
1 mL min 1), UV: 220 nm, tmajor = 15.74, tminor = 10.24 min; [a]20
D = 1.0
(c = 0.61 in CHCl3); 1H NMR (400 MHz, CDCl3 + [D]DMSO): d = 7.59–
7.57 (m, 2 H), 7.52–7.49 (m, 1 H), 7.42–7.36 (m, 2 H), 7.17–7.15 (m,
4 H), 7.09–7.06 (m, 1 H), 3.46–3.43 (m, 1 H), 2.82–2.78 (m, 1 H), 2.63–
2.53 (m, 3 H), 2.29–2.23 (m, 1 H), 2.13 ppm (d, J = 12 Hz, 1 H);
13
C NMR (100 MHz, CDCl3): d = 205.9, 143.4, 142.5, 135.8, 132.8,
129.1, 128.3, 126.5, 122.6, 120.7, 120.7, 64.7, 50.8, 47.0, 43.4,
38.9 ppm; ESI-HRMS: calcd for C18H17NO3S + Na + : 350.0821; found:
350.0829.
Scheme 6. Proposed catalytic transition state for asymmetric formal [3+3] (1’S,2’S,4’R,5’S)-2’,4’-Dimethyl-5’-phenyl-2H-spiro(benzo[d]i-
cycloaddition. sothiazole-3,1’-cyclohexan)-3’-one 1,1-dioxide (4 b)
Obtained as a white solid in 78 % yield after flash chromatography
and the enantiomeric excess was determined to be 98 % by HPLC
ed for unsymmetrical ketones with diverse substitutions. These analysis on Chiralpak IA column (40 % 2-propanol/n-hexane,
chiral frameworks with high molecular and stereogenic com- 1 mL min 1), UV: 220 nm, tmajor = 30.32, tminor = 23.54 min; [a]20 D =
plexity might find further application in organic synthesis and 8.1 (c = 0.88 in CHCl3); 1H NMR (400 MHz, CDCl3): d = 7.77 (d, J =
medicinal chemistry. 7.6 Hz, 1 H), 7.69 (t, J = 7.6 Hz, 1 H), 7.56 (t, J = 7.6 Hz, 1 H), 7.51 (d,
J = 8.0 Hz, 1 H), 7.35–7.31 (m, 2 H), 7.25–7.22 (m, 3 H), 4.57 (s, 1 H),
3.33 (q, J = 6.8 Hz, 1 H), 3.02 (td, J = 12.0, 3.6 Hz, 1 H), 2.96–2.89 (m,
1 H), 2.50–2.44 (m, 1 H), 2.29 (dd, J = 14.0, 3.6 Hz, 1 H), 0.92 (d, J =
Experimental Section 6.0 Hz, 3 H), 0.86 ppm (d, J = 6.8 Hz, 3 H); 13C NMR (100 MHz, CDCl3):
General 209.3, 141.6, 141.5, 135.4, 133.7, 129.9, 128.8, 127.4, 127.2, 122.7,
121.7, 70.0, 51.6, 50.3, 49.3, 47.4, 12.2, 8.0 ppm; ESI-HRMS: calcd for
NMR spectra were recorded with tetramethylsilane as the internal C20H21NO3S + Na + : 378.1134; found: 378.1139.
standard. 1H NMR spectra were recorded at 400 or 600 MHz and
13
C NMR spectra were recorded at 100 or 150 MHz. Chemical shifts
(1’S,4’R,5’R)-4’-[(tert-Butyldimethylsilyl)oxy]-5’-phenyl-2H-spi-
are reported in ppm downfield from CDCl3 (d = 7.26 ppm) for
1 ro(benzo[d]isothiazole-3,1’-cyclohexan)-3’-one 1,1-dioxide
H NMR and relative to the central CDCl3 resonance (d = 77.0 ppm)
for 13C NMR spectroscopy. Coupling constants are given in Hz. (4 f)
Enantiomeric excess was determined by HPLC analysis on Daicel Obtained as a white solid in 85 % yield after flash chromatography
Chiralpak AD-H Column (250 4.6 mm) or Chiralpak OD-H Column and the enantiomeric excess was determined to be 96 % by HPLC
(250 4.6 mm), Chiralpak IA Column (250 4.6 mm), Chiralpak IB analysis on Chiralpak AD-H column (40 % 2-propanol/n-hexane,
Column (250 4.6 mm), Chiralpak IC Column (250 4.6 mm). UV de- 1 mL min 1), UV: 220 nm, tmajor = 5.34, tminor = 6.73 min; [a]20D = + 50.7
tection was monitored at 220 or 254 nm. TLC analysis was per- (c = 0.84 in CHCl3); 1H NMR (400 MHz, CDCl3): d = 7.77 (d, J = 7.2 Hz,
formed on glass-backed silica plates. UV light and I2 were used to 1 H), 7.70 (t, J = 6.8 Hz, 1 H), 7.59–7.53 (m, 2 H), 7.33–7.22 (m, 5 H),
visualize products. Column chromatography was performed using 4.93 (s, 1 H), 4.44 (d, J = 10.8 Hz, 1 H), 3.40 (td, J = 12.0, 3.6 Hz, 1 H),
silica gel (200–300 mesh) eluting with EtOAc/petroleum ether and 3.24 (d, 14.0 Hz, 1 H), 2.73 (dd, J = 14.0, 3.6 Hz, 1 H), 2.62–2.55 (m,
acetone/dichloromethane). Optical rotations were measured at 1 H), 2.31 (dt, J = 14.0, 3.6 Hz, 1 H), 0.64 (s, 9 H), 0.04 (s, 3 H),
589 nm at 20 8C. Unless otherwise noted, commercial reagents 0.38 ppm (s, 3 H); 13C NMR (150 MHz, CDCl3): 204.5, 142.7, 140.2,
were used as received and all reactions were carried out directly 135.8, 133.6, 130.0, 128.5, 128.1, 127.3, 122.7, 121.6, 81.0, 65.4, 50.6,
under an air atmosphere. 3-Vinyl-1,2-benzoisothiazol-1,1-dioxides 3 49.5, 43.3, 25.4, 18.1, 6.1, 6.2 ppm; ESI-HRMS: calcd for
and 4-styryl-1,2,3-benzoxathiazine-2,2-dioxide 6 were prepared ac- C24H31NO4SSi + Na + : 480.1635; found: 480.1640.
cording to the literature procedures.[8, 17] The primary amines
1 were also synthesized according to the literature procedures.[21]
(1’S,3’S)-3’-(Furan-2-yl)-2H-spiro(benzo[d]isothiazole-3,1’-cy-
clohexan)-5’-one 1,1-dioxide (4 q)
Typical procedure for asymmetric formal [3+3] cycloaddi-
Obtained as a white solid in 78 % yield after flash chromatography
tion
and the enantiomeric excess was determined to be 60 % by HPLC
The reaction was carried out with 1-azadiene 3 (0.1 mmol), catalyst analysis on Chiralpak OD-H column (40 % 2-propanol/n-hexane,
1 a (0.02 mmol), and salicylic acid (0.04 mmol) in corresponding 1 mL min 1), UV: 220 nm, tmajor = 14.36, tminor = 9.72 min; [a]20
D = 4.2
ketone (1.0 mL) at room temperature or 40 8C (unless otherwise (c = 0.29 in CHCl3); 1H NMR (400 MHz, CDCl3): d = 7.80 (d, J = 8.0 Hz,
noted). After completion, the solution was concentrated and the 1 H), 7.69 (t, J = 7.6 Hz, 1 H), 7.58 (t, J = 7.6 Hz, 1 H), 7.49 (d, J =
& & Chem. Eur. J. 2015, 21, 1 – 7 www.chemeurj.org 4 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
7.6 Hz, 1 H), 7.33–7.26 (m, 1 H), 6.29 (br s, 1 H), 6.08 (d, J = 2.8 Hz, 2010, 29, 2126; f) X. Wang, X. Xu, P. Y. Zavalij, M. P. Doyle, J. Am. Chem.
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& & Chem. Eur. J. 2015, 21, 1 – 7 www.chemeurj.org 6 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
FULL PAPER
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