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J Am Chem Soc. 2015 Jul 1;137(25):8006-9. doi: 10.1021/jacs.5b04429. Epub 2015 Jun 18.

Asymmetric Annulation of Donor-Acceptor Cyclopropanes with Dienes.

Author information

1
‡State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
2
§Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, China.

Abstract

An efficient [4 + 3] cycloaddition reaction of D-A cyclopropanes with dienes has been successfully developed. The reaction proceeds well with various dienolsilyl ethers in the presence of Lewis acid, delivering a variety of cycloheptenes and [n,5,0]carbobicycles with excellent stereoselectivity. The asymmetric version of this reaction is also realized using a newly designed chiral Cy-TOX ligand, providing a new approach to access optically active cycloheptenes and [n,5,0]carbobicycles. Mechanisic study reveals that the reaction involves a stepwise pathway, which undergoes an unusual ring opening of five-membered [3 + 2] intermediate and sequential intramolecular cyclization to afford the thermodynamically stable [4 + 3] annulation product.

PMID:
26068395
DOI:
10.1021/jacs.5b04429
[Indexed for MEDLINE]

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