A Direct Synthesis of Alkenyl Alkylidene Bicyclo[3.1.0]hexane Derivatives via Ruthenium(II)-Catalysed Bicyclisation of Allenynes

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.

allenynes - C-C coupling cyclisation - homogeneous catalysis - ruthenium

References and Notes

<A NAME="RG36007ST-1">1</A> Brandi A. Goti A. Chem. Rev.  1998,  98:  589 

<A NAME="RG36007ST-2">2</A> Nakamura I. Yamamoto Y. Adv. Synth. Catal.  2002,  344:  111 

<A NAME="RG36007ST-3A">3a</A> Noyori R. Odagi T. Takaya H. J. Am. Chem. Soc.  1970,  92:  5780 

<A NAME="RG36007ST-3B">3b</A> Binger P. Wedemann P. Tetrahedron Lett.  1983,  24:  5847 

<A NAME="RG36007ST-3C">3c</A> Binger P. Doyle MJ. Benn R. Chem. Ber.  1983,  116:  1 

<A NAME="RG36007ST-3D">3d</A> Trost BM. Angew. Chem., Int. Ed. Engl.  1986,  25:  1 

<A NAME="RG36007ST-3E">3e</A> Yamago S. Nakamura E. J. Chem. Soc., Chem. Commun.  1988,  1112 

<A NAME="RG36007ST-4A">4a</A> Lautens M. Ren Y. Delanghe PHM. J. Am. Chem. Soc.  1994,  116:  8821 

<A NAME="RG36007ST-4B">4b</A> Corlay H. Lewis RT. Motherwell WB. Shipman M. Tetrahedron  1995,  51:  3303 

<A NAME="RG36007ST-4C">4c</A> De Meijere A. Nüske H. Es-Sayed M. Labahn T. Schroen M. Bräse S. Angew. Chem. Int. Ed.  1999,  38:  3669 

<A NAME="RG36007ST-4D">4d</A> Nüske H. Notlemeyer M. De Meijere A. Angew. Chem. Int. Ed.  2001,  40:  3411 

<A NAME="RG36007ST-5">5</A> Binger P. Freund A. Wedemann P. Tetrahedron  1989,  45:  2887 

<A NAME="RG36007ST-6A">6a</A> Binger P. Weintz H.-J. Chem. Ber.  1984,  117:  654 

<A NAME="RG36007ST-6B">6b</A> Oh B.-H. Nakamura I. Saito S. Yamamoto Y. Tetrahedron Lett.  2001,  42:  6203 

<A NAME="RG36007ST-6C">6c</A> Murakami M. Ishida N. Miura T. Chem. Commun.  2006,  643 

<A NAME="RG36007ST-7">7</A> Itazaki M. Nishihara Y. Takimoto H. Yoda C. Osakada K. J. Mol. Catal. A: Chem.  2005,  241:  65 

<A NAME="RG36007ST-8">8</A> Tsukada N. Shibuya A. Nakamura I. Kitahara H. Yamamoto Y. Tetrahedron  1999,  55:  8833 

<A NAME="RG36007ST-9">9</A> Kurahashi T. De Meijere A. Angew. Chem. Int. Ed.  2005,  44:  7881 

<A NAME="RG36007ST-10A">10a</A> Nakamura I. Itagaki H. Yamamoto Y. J. Org. Chem.  1998,  63:  6458 

<A NAME="RG36007ST-10B">10b</A> Yamamoto T. Sano K. Yamamoto A. Chem. Lett.  1982,  907 

<A NAME="RG36007ST-10C">10c</A> Seligson AL. Cowan RL. Trogler WC. Inorg. Chem.  1991,  30:  3371 

<A NAME="RG36007ST-11">11</A> Shi M. Liu L.-P. Tang J. Org. Lett.  2006,  8:  4043 

<A NAME="RG36007ST-12">12</A> Lian J.-J. Odedra A. Wu C.-J. Liu R.-S. J. Am. Chem. Soc.  2005,  127:  4186 

<A NAME="RG36007ST-13">13</A> Kamikawa K. Shimizu Y. Takemoto S. Matsuzaka H. Org. Lett.  2006,  8:  4011 

<A NAME="RG36007ST-14">14</A> Shi M. Liu L.-P. Tang J. J. Am. Chem. Soc.  2006,  128:  7430 

<A NAME="RG36007ST-15">15</A> Fürstner A. Aïssa C. J. Am. Chem. Soc.  2006,  128:  6306 

<A NAME="RG36007ST-16A">16a</A> Stang PJ. Chem. Rev.  1978,  78:  383 ; and cited references

<A NAME="RG36007ST-16B">16b</A> Gajewski JJ. Paul GC. Chang MJ. Gortva AM. J. Am. Chem. Soc.  1994,  116:  5150 

<A NAME="RG36007ST-17A">17a</A> Köster R. Arora S. Binger P. Justus Liebigs Ann. Chem.  1973,  1219 

<A NAME="RG36007ST-17B">17b</A> Muthuramu K. Ramamurthy V. J. Chem. Soc., Chem. Commun.  1980,  243 

<A NAME="RG36007ST-18A">18a</A> Dolbier WR. Seabury M. Daly D. Smart BE. J. Org. Chem.  1986,  51:  974 

<A NAME="RG36007ST-18B">18b</A> Loosli T. Borer M. Kulakowska I. Minger A. Neuenschwander M. Engel P. Helv. Chim. Acta  1995,  78:  1144 ; and cited references

<A NAME="RG36007ST-19A">19a</A> Rousseau G. Le Percher P. Conia JM. Tetrahedron Lett.  1977,  45 

<A NAME="RG36007ST-19B">19b</A> Wessjohann L. Giller K. Zuck B. Skattebal L. De Meijere A. J. Org. Chem.  1993,  58:  6442 

<A NAME="RG36007ST-19C">19c</A> Padwa A. Wannamaker MW. Tetrahedron  1991,  47:  6139 

<A NAME="RG36007ST-19D">19d</A> Stolle A. Ollivier J. Piras PP. Salaün J. De Meijere A. J. Am. Chem. Soc.  1992,  114:  4051 

<A NAME="RG36007ST-20A">20a</A> Bestmann H.-J. Denzel T. Tetrahedron Lett.  1966,  3591 

<A NAME="RG36007ST-20B">20b</A> Schweizer EE. Thompson JG. J. Chem. Soc., Chem. Commun.  1966,  666 

<A NAME="RG36007ST-20C">20c</A> Stafford JA. McMurry JE. Tetrahedron Lett.  1988,  29:  2531 

<A NAME="RG36007ST-20D">20d</A> Maercker A. Daub VEE. Tetrahedron  1994,  50:  2439 

<A NAME="RG36007ST-21">21</A> Monnier F. Castillo D. Dérien S. Toupet L. Dixneuf PH. Angew. Chem. Int. Ed.  2003,  42:  5474 

<A NAME="RG36007ST-22">22</A> Monnier F. Vovard-Le Bray C. Castillo D. Aubert V. Dérien S. Dixneuf PH. Toupet L. Ienco A. Mealli C. J. Am. Chem. Soc.  2007,  129:  6037 

<A NAME="RG36007ST-23">23</A> Murakami M. Kadowaki S. Matsuda T. Org. Lett.  2005,  7:  3953 

<A NAME="RG36007ST-24A">24a</A> Trost BM. Pinkerton AB. J. Am. Chem. Soc.  1999,  121:  4068 

<A NAME="RG36007ST-24B">24b</A> Trost BM. Pinkerton AB. Seidel M. J. Am. Chem. Soc.  2001,  123:  12466 

<A NAME="RG36007ST-25">25</A> Bustelo E. Guerot C. Hercouet A. Carboni B. Toupet L. Dixneuf PH. J. Am. Chem. Soc.  2005,  127:  11582 

<A NAME="RG36007ST-26">26</A>

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.

<A NAME="RG36007ST-27A">27a</A> Wegner HA. De Meijere A. Wender PA. J. Am. Chem. Soc.  2005,  127:  6530 

<A NAME="RG36007ST-27B">27b</A> Wender PA. Haustedt LO. Lim J. Love JA. Williams TJ. Yoon J.-Y. J. Am. Chem. Soc.  2006,  128:  6302