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

Chloé Vovard-Le Bray; Sylvie Dérien; Pierre H. Dixneuf; Masahiro Murakami

doi:10.1055/s-2008-1032015

RSS-Feed abonnieren

Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.

https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000083.xml

Teilen / Bookmarken

Facebook X Linkedin Weibo

PDF herunterladen

Synlett 2008(2): 193-196
DOI: 10.1055/s-2008-1032015

LETTER

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

Chloé Vovard-Le Bray^a, Sylvie Dérien^a, Pierre H. Dixneuf*^a, Masahiro Murakami*^b
^a Laboratoire ‘catalyse et organométalliques’, Institut Sciences Chimiques de Rennes, UMR 6226 CNRS Université de Rennes 1, Campus de Beaulieu, 35042 Rennes, France
Fax: +33(223)236939; e-Mail: pierre.dixneuf@univ-rennes1.fr;
^b Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Katsura, Kyoto 615-8510, Japan

Weitere Informationen

Publikationsverlauf

Received 26 October 2007
Publikationsdatum:
04. Januar 2008 (online)

Abstract
Volltext
Referenzen

Lizenzen und Reprints Alle Artikel dieser Rubrik

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

References and Notes

1 Brandi A. Goti A. Chem. Rev. 1998, 98: 589

Crossref PubMed Google Scholar
2 Nakamura I. Yamamoto Y. Adv. Synth. Catal. 2002, 344: 111

Crossref Google Scholar
3a Noyori R. Odagi T. Takaya H. J. Am. Chem. Soc. 1970, 92: 5780

Crossref Google Scholar
3b Binger P. Wedemann P. Tetrahedron Lett. 1983, 24: 5847

Crossref Google Scholar
3c Binger P. Doyle MJ. Benn R. Chem. Ber. 1983, 116: 1

Crossref Google Scholar
3d Trost BM. Angew. Chem., Int. Ed. Engl. 1986, 25: 1

Crossref Google Scholar
3e Yamago S. Nakamura E. J. Chem. Soc., Chem. Commun. 1988, 1112

Crossref Google Scholar
4a Lautens M. Ren Y. Delanghe PHM. J. Am. Chem. Soc. 1994, 116: 8821

Crossref Google Scholar
4b Corlay H. Lewis RT. Motherwell WB. Shipman M. Tetrahedron 1995, 51: 3303

Crossref Google Scholar
4c De Meijere A. Nüske H. Es-Sayed M. Labahn T. Schroen M. Bräse S. Angew. Chem. Int. Ed. 1999, 38: 3669

Crossref Google Scholar
4d Nüske H. Notlemeyer M. De Meijere A. Angew. Chem. Int. Ed. 2001, 40: 3411

Crossref Google Scholar
5 Binger P. Freund A. Wedemann P. Tetrahedron 1989, 45: 2887

Crossref Google Scholar
6a Binger P. Weintz H.-J. Chem. Ber. 1984, 117: 654

Crossref Google Scholar
6b Oh B.-H. Nakamura I. Saito S. Yamamoto Y. Tetrahedron Lett. 2001, 42: 6203

Crossref Google Scholar
6c Murakami M. Ishida N. Miura T. Chem. Commun. 2006, 643

Crossref Google Scholar
7 Itazaki M. Nishihara Y. Takimoto H. Yoda C. Osakada K. J. Mol. Catal. A: Chem. 2005, 241: 65

Crossref Google Scholar
8 Tsukada N. Shibuya A. Nakamura I. Kitahara H. Yamamoto Y. Tetrahedron 1999, 55: 8833

Crossref Google Scholar
9 Kurahashi T. De Meijere A. Angew. Chem. Int. Ed. 2005, 44: 7881

Crossref Google Scholar
10a Nakamura I. Itagaki H. Yamamoto Y. J. Org. Chem. 1998, 63: 6458

Crossref Google Scholar
10b Yamamoto T. Sano K. Yamamoto A. Chem. Lett. 1982, 907

Crossref Google Scholar
10c Seligson AL. Cowan RL. Trogler WC. Inorg. Chem. 1991, 30: 3371

Crossref Google Scholar
11 Shi M. Liu L.-P. Tang J. Org. Lett. 2006, 8: 4043

Crossref PubMed Google Scholar
12 Lian J.-J. Odedra A. Wu C.-J. Liu R.-S. J. Am. Chem. Soc. 2005, 127: 4186

Crossref Google Scholar
13 Kamikawa K. Shimizu Y. Takemoto S. Matsuzaka H. Org. Lett. 2006, 8: 4011

Crossref Google Scholar
14 Shi M. Liu L.-P. Tang J. J. Am. Chem. Soc. 2006, 128: 7430

Google Scholar
15 Fürstner A. Aïssa C. J. Am. Chem. Soc. 2006, 128: 6306

Google Scholar
16a Stang PJ. Chem. Rev. 1978, 78: 383 ; and cited references

Crossref Google Scholar
16b Gajewski JJ. Paul GC. Chang MJ. Gortva AM. J. Am. Chem. Soc. 1994, 116: 5150

Crossref Google Scholar
17a Köster R. Arora S. Binger P. Justus Liebigs Ann. Chem. 1973, 1219

Crossref Google Scholar
17b Muthuramu K. Ramamurthy V. J. Chem. Soc., Chem. Commun. 1980, 243

Crossref Google Scholar
18a Dolbier WR. Seabury M. Daly D. Smart BE. J. Org. Chem. 1986, 51: 974

Crossref Google Scholar
18b Loosli T. Borer M. Kulakowska I. Minger A. Neuenschwander M. Engel P. Helv. Chim. Acta 1995, 78: 1144 ; and cited references

Crossref Google Scholar
19a Rousseau G. Le Percher P. Conia JM. Tetrahedron Lett. 1977, 45

Crossref Google Scholar
19b Wessjohann L. Giller K. Zuck B. Skattebal L. De Meijere A. J. Org. Chem. 1993, 58: 6442

Crossref Google Scholar
19c Padwa A. Wannamaker MW. Tetrahedron 1991, 47: 6139

Crossref Google Scholar
19d Stolle A. Ollivier J. Piras PP. Salaün J. De Meijere A. J. Am. Chem. Soc. 1992, 114: 4051

Crossref Google Scholar
20a Bestmann H.-J. Denzel T. Tetrahedron Lett. 1966, 3591

Crossref Google Scholar
20b Schweizer EE. Thompson JG. J. Chem. Soc., Chem. Commun. 1966, 666

Crossref Google Scholar
20c Stafford JA. McMurry JE. Tetrahedron Lett. 1988, 29: 2531

Crossref Google Scholar
20d Maercker A. Daub VEE. Tetrahedron 1994, 50: 2439

Crossref Google Scholar
21 Monnier F. Castillo D. Dérien S. Toupet L. Dixneuf PH. Angew. Chem. Int. Ed. 2003, 42: 5474

Crossref PubMed Google Scholar
22 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

Crossref PubMed Google Scholar
23 Murakami M. Kadowaki S. Matsuda T. Org. Lett. 2005, 7: 3953

Crossref Google Scholar
24a Trost BM. Pinkerton AB. J. Am. Chem. Soc. 1999, 121: 4068

Crossref Google Scholar
24b Trost BM. Pinkerton AB. Seidel M. J. Am. Chem. Soc. 2001, 123: 12466

Crossref Google Scholar
25 Bustelo E. Guerot C. Hercouet A. Carboni B. Toupet L. Dixneuf PH. J. Am. Chem. Soc. 2005, 127: 11582

Crossref PubMed Google Scholar
27a Wegner HA. De Meijere A. Wender PA. J. Am. Chem. Soc. 2005, 127: 6530

Crossref Google Scholar
27b Wender PA. Haustedt LO. Lim J. Love JA. Williams TJ. Yoon J.-Y. J. Am. Chem. Soc. 2006, 128: 6302

Crossref Google Scholar

26

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.