Tandem cyclopropanation/ring-closing metathesis of dienynes

Journal of the American Chemical Society

Volumn 126, Issue 31, 2004, Pages 9524-9525

  Peppers, Brian P ^a   Diver, Steven T ^a  

^a UNIVERSITY AT BUFFALO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBENE; CYCLOPROPANE; METAL COMPLEX; RUTHENIUM COMPLEX;

ARTICLE; CATALYSIS; CYCLOADDITION; CYCLOPROPANATION; REACTION ANALYSIS; RING CLOSING METATHESIS;

ALKENES; ALKYNES; CATALYSIS; CYCLIZATION; CYCLOPENTANES; CYCLOPROPANES; RUTHENIUM;

EID: 3543131388     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja049079o     Document Type: Article

References (20)

1. Reviews: (a) Aubert, C.; Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813-834.
2. (b) Schmidt, B. Angew. Chem., Int. Ed. 2003, 42, 4996-4999.
3. (c) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317-1382.
4. (d) First report using Pd(II): Trost, B. M.; Tanoury, G. J. J. Am. Chem. Soc. 1988, 110, 1636-1638.
5. A notable exception is the coordinatively saturated Ru(II) carbene of Nishiyama that gives cyclopropanation: (a) Nishiyama, H.; Itoh, Y.; Matsumoto, H.; Park, S.-B.; Itoh, K. J. Am. Chem. Soc. 1994, 116, 2223-2224.
6. Reductive elimination of noncarbene Ru(II) from Ru(IV) ruthenacyclobutanes has been suggested as a competing process that consumes propagating metal carbenes. See: (b) Kinoshita, A.; Mori, M. Synlett 1994, 1020-1022.
7. (c) Kitamura, T.; Sato, Y.; Mori, M. Chem. Commun. 2001, 1258-1259.
8. 1H NMR include < 1 % of the eight-membered ring (see 12A, eq 3) and showed 1 to 2% aromatization of 3A.
9. 1H NMR reveals ca. 2 to 3% unreacted 1C, no styrene and 1 to 2% dimeric byproduct (see 14).
10. (a) Semeril, D.; Bruneau, C.; Dixneuf, P. H. Helv. Chim. Acta 2001, 84, 3335-3341.
11. (b) Semeril, D.; Bruneau, C.; Dixneuf, P. H. Adv. Synth. Catal. 2002, 344, 585-595.
12. 3P, the in situ catalyst (20 mol %) gave incomplete conversion: 40% 1C, 5-10% 2C.
13. Carbene generation by 1-alkyne to vinylidene carbene rearrangement is discounted since allenes were not detected and because regeneration of a carbene would consume 50 mol % of dienyne, restricting yields to 50%.
14. Related carbenoid trapping for polycyclic ring synthesis: Chatani, N.; Kataoka, K.; Murai, S.; Furukawa, N.; Seki, Y. J. Am. Chem. Soc. 1998, 120, 9104-9105.
15. Chatani, N.; Inoue, H.; Kotsuma, T.; Murai, S. J. Am. Chem. Soc. 2002, 124, 10294-10295.
16. (a) Fürstner, A.; Szillat, H.; Gabor, B.; Mynott, R. J. Am. Chem. Soc. 1998, 120, 8305-8314.
17. (b) Fürstner, A.; Szillat, H.; Stelzer, F. J. Am. Chem. Soc. 2000, 122, 6785-6786.
18. (a) Diene 16 could also arise by reductive elimination from a ruthenacyclobutane.
19. (b) A bidentate, cyclometallative pathway is also possible for the right side of Scheme 2.
20. This is an important difference between the parallel studies of Dixneuf, where the metal carbene was regenerated with added diazoalkane. See: Monnier, F.; Castillo, D.; Derien, S.; Toupet, L.; Dixneuf, P. H. Angew. Chem., Int. Ed. 2003, 42, 5474-5477.