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DOI: 10.1055/s-2008-1032015
A Direct Synthesis of Alkenyl Alkylidene Bicyclo[3.1.0]hexane Derivatives via Ruthenium(II)-Catalysed Bicyclisation of Allenynes
Publication History
Publication Date:
04 January 2008 (online)
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Abstract
The reaction of allenynes with N2CHSiMe3 in the presence of RuCl(cod)Cp* catalyst at room temperature constitutes a selective, general route to alkylidenebicyclo[3.1.0]hexanes having an adjacent Z-CH=CHSiMe3 group. The reaction shows that the RuCl(Cp*) moiety favours reductive elimination of a metallacyclobutane intermediate and not the enyne metathesis process.
Keywords
allenynes - C-C coupling cyclisation - homogeneous catalysis - ruthenium
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References and Notes
Low isolated product yields were obtained only when the reaction was performed with a small substrate quantity (0.1 mmol) due to inefficient extraction techniques for small quantities; for example, for 1c 40% and 85% isolated yields were obtained from 0.1 mmol and 0.3 mmol, respectively.
Typical Procedure for the Catalytic Reaction: In a Schlenk tube under an inert atmosphere, to a solution of the allenyne in degassed Et2O (1.5 mL) was added the (trimethylsilyl)diazomethane solution (2.0 M; 1.1 equiv) in Et2O. Next, the precatalyst RuCl(cod)Cp* (8 mol%) was introduced. The mixture was stirred at r.t. Reaction completion was monitored using TLC or 1H NMR techniques. The products were obtained after purification by silica gel chromatography with an Et2O-pentane eluting mixture.
Data for compounds 2a-d, 4a,b, and 6:
Compound 2a: 1H NMR (300.13 MHz, CDCl3): δ = 0.12 (s, 9 H, SiMe3), 1.68 (s, 3 H, Me), 1.69 (s, 3 H, Me), 1.95 (m, 1 H, CH), 2.45 (s, 3 H, Me), 3.26 (dd, J = 4.1, 9.4 Hz, 1 H, NCH2), 3.27 (d, J = 9.0 Hz, 1 H, NCH2), 3.64 (d, J = 9.4 Hz, 1 H, NCH2), 3.80 (d, J = 9.1 Hz, 1 H, NCH2), 5.49 (d, J = 15.6 Hz, 1 H, =CHSiMe3), 6.02 (d, J = 15.6 Hz, 1 H, CH=), 7.32 (d, J = 7.8 Hz, 2 H, Ph), 7.67 (d, J = 8.2 Hz, 2 H, Ph). 13C NMR (75.47 MHz, CDCl3): δ = 145.1, 143.3, 133.7, 129.5, 129.4, 127.6, 127.5, 122.3, 53.1, 50.0, 35.9, 29.9, 22.2, 21.6, 21.5, 0.8. HRMS: m/z calcd for C20H29NO2SiS: 375.1688; found: 375.1684.
Compound 2b (two isomers, 55:45): Major isomer: 1H NMR (300.08 MHz, CDCl3): δ = 0.11 (s, 9 H, SiMe3), 0.97 (t, J = 7.7 Hz, 3 H, Me), 1.70 (s, 3 H, Me), 1.91 (m, 1 H, CH), 1.99 (m, 2 H, CH2), 2.45 (s, 3 H, Me), 3.24 (m, 1 H, NCH2), 3.28 (d, J = 9.0 Hz, 1 H, NCH2), 3.65 (d, J = 9.2 Hz, 1 H, NCH2), 3.75 (d, J = 9.0 Hz, 1 H, NCH2), 5.47 (d, J = 15.6 Hz, 1 H, =CHSiMe3), 6.01 (d, J = 15.6 Hz, 1 H, CH=), 7.32 (d, J = 7.9 Hz, 2 H, Ph), 7.68 (d, J = 8.2 Hz, 2 H, Ph). 13C NMR (75.47 MHz, CDCl3): δ = 145.4, 143.3, 133.8, 133.0, 129.5, 129.2, 127.6, 121.2, 53.1, 50.5, 36.3, 30.5, 29.2, 21.5, 20.1, 12.0, 0.8. Minor isomer: 1H NMR (300.08 MHz, CDCl3): δ = 0.13 (s, 9 H, SiMe3), 1.02 (t, J = 7.4 Hz, 3 H, Me), 1.62 (s, 3 H, Me), 1.99 (m, 2 H, CH2), 2.01 (m, 1 H, CH), 2.45 (s, 3 H, Me), 3.24 (m, 1 H, NCH2), 3.28 (d, J = 9.0 Hz, 1 H, NCH2), 3.63 (d, J = 9.1 Hz, 1 H, NCH2), 3.81 (d, J = 8.9 Hz, 1 H, NCH2), 5.49 (d, J = 15.6 Hz, 1 H, =CHSiMe3), 6.00 (d, J = 15.5 Hz, 1 H, CH=), 7.32 (d, J = 7.9 Hz, 2 H, Ph), 7.68 (d, J = 8.2 Hz, 2 H, Ph). 13C NMR (75.47 MHz, CDCl3): δ = 145.8, 143.3, 133.2, 133.0, 129.5, 128.9, 127.6, 121.5, 53.4, 50.0, 36.3, 29.4, 28.7, 21.5, 20.5, 12.4, 0.8. HRMS: m/z calcd for C21H31NO2SiS: 389.1845; found: 389.1854.
Compound 2c: 1H NMR (200.13 MHz, CDCl3): δ = 0.11 (s, 9 H, SiMe3), 1.06 (m, 12 H, Me), 1.94 (m, 1 H, CH), 2.38 (m, 2 H, CH), 2.44 (s, 3 H, Me), 3.19 (dd, J = 4.1, 8.8 Hz, 1 H, NCH2), 3.25 (d, J = 8.3 Hz, 1 H, NCH2), 3.64 (d, J = 8.8 Hz, 1 H, NCH2), 3.72 (d, J = 8.5 Hz, 1 H, NCH2), 5.45 (d, J = 15.7 Hz, 1 H, =CHSiMe3), 5.94 (d, J = 15.7 Hz, 1 H, CH=), 7.32 (d, J = 7.7 Hz, 2 H, Ph), 7.70 (d, J = 8.1 Hz, 2 H, Ph). 13C NMR (75.47 MHz, CDCl3): δ = 148.3, 146.9, 143.4, 133.7, 129.5, 127.7, 127.6, 119.0, 53.1, 50.5, 33.8, 33.6, 32.9, 28.5, 22.9, 22.6, 22.5, 22.2, 21.5, 1.0. HRMS: m/z calcd for C24H37NO2SiS: 431.2314; found: 431.2304.
Compound 2d: 1H NMR (300.08 MHz, CDCl3): δ = 0.12 (s, 9 H, SiMe3), 1.50 (m, 6 H, CH2), 1.98 (m, 1 H, CH), 2.07 (m, 4 H, CH2), 2.45 (s, 3 H, Me), 3.23 (dd, J = 4.1, 13.2 Hz, 1 H, NCH2), 3.26 (d, J = 8.6 Hz, 1 H, NCH2), 3.61 (d, J = 9.2 Hz, 1 H, NCH2), 3.76 (d, J = 8.8 Hz, 1 H, NCH2), 5.48 (d, J = 15.6 Hz, 1 H, =CHSiMe3), 6.04 (d, J = 15.5 Hz, 1 H, CH=), 7.33 (d, J = 7.9 Hz, 2 H, Ph), 7.68 (d, J = 8.2 Hz, 2 H, Ph). 13C NMR (75.47 MHz, CDCl3): δ = 145.5, 143.3, 135.3, 133.8, 129.6, 129.1, 127.6, 119.1, 53.2, 50.1, 47.5, 35.4, 33.2, 32.8, 29.3, 27.7, 26.4, 21.5, 0.8. HRMS: m/z calcd for C23H33NO2SiS: 415.2001; found: 415.1994.
Compound 4a: 1H NMR (200.13 MHz, CDCl3): δ = 0.13 (s, 9 H, SiMe3), 1.20 (s, 3 H, Me), 1.53 (s, 3 H, Me), 1.94 (m, 1 H, CH), 2.44 (s, 3 H, Me), 3.46 (dd, J = 4.1, 9.7 Hz, 1 H, NCH2), 3.48 (d, J = 9.2 Hz, 1 H, NCH2), 3.60 (d, J = 9.6 Hz, 1 H, NCH2), 4.06 (d, J = 9.2 Hz, 1 H, NCH2), 5.60 (s, 1 H, =CHSiMe3), 7.07 (m, 2 H, Ph), 7.31 (m, 5 H, Ph + Ts), 7.78 (d, J = 8.2 Hz, 2 H, Ts). 13C NMR (75.47 MHz, CDCl3): δ = 155.2, 146.6, 143.2, 134.3, 132.5, 129.5, 127.8, 127.4, 126.8, 126.7, 120.3, 55.4, 50.3, 38.4, 28.0, 22.7, 21.5, 20.9, 0.8. HRMS: m/z calcd for C26H33NO2SiS: 451.2001; found: 451.2008.
Compound 4b: 1H NMR (200.13 MHz, CDCl3): δ = 0.13 (s, 9 H, SiMe3), 1.24 (s, 3 H, Me), 1.54 (s, 3 H, Me), 1.95 (m, 1 H, CH), 2.44 (s, 3 H, Me), 3.44 (dd, J = 4.1, 9.5 Hz, 1 H, NCH2), 3.46 (d, J = 9.5 Hz, 1 H, NCH2), 3.60 (d, J = 9.1 Hz, 1 H, NCH2), 3.79 (s, 3 H, OMe), 4.04 (d, J = 9.1 Hz, 1 H, NCH2), 5.61 (s, 1 H, =CHSiMe3), 6.70 (m, 3 H, p-C6H4OMe), 7.29 (m, 3 H, p-C6H4OMe + Ph), 7.67 (d, J = 8.2 Hz, 2 H, Ph). 13C NMR (75.47 MHz, CDCl3): δ = 158.2, 154.2, 147.2, 142.7, 142.4, 131.5, 128.7, 126.6, 118.5, 54.6, 54.4, 49.5, 37.4, 27.2, 20.7, 20.2, 19.5, 0.0. HRMS: m/z calcd for C27H35NO3SiS: 481.2107; found: 481.2101.
Compound 6: 1H NMR (300.13 MHz, CDCl3): δ = 0.20 (s, 9 H, SiMe3), 1.67 (s, 3 H, Me), 1.71 (s, 3 H, Me), 1.89 (m, 1 H, CH), 2.35 (dd, J = 4.6, 12.6 Hz, 1 H, NCH2), 2.50 (d, J = 12.3 Hz, 1 H, NCH2), 2.81 (d, J = 12.6 Hz, 1 H, NCH2), 3.03 (d, J = 12.3 Hz, 1 H, NCH2), 3.64 (s, 3 H, OMe), 3.70 (s, 3 H, OMe), 5.44 (d, J = 15.5 Hz, 1 H, =CHSiMe3), 6.11 (d, J = 15.5 Hz, 1 H, CH=). 13C NMR (75.47 MHz, CDCl3): δ = 172.0, 171.2, 148.4, 128.1, 127.1, 125.0, 59.4, 52.9, 52.6, 39.7, 36.1, 35.9, 29.8, 22.2, 21.5, 1.20. HRMS: m/z calcd for C18H28O4Si: 336.1757; found: 336.1750.