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Synthesis 2014; 46(16): 2220-2224
DOI: 10.1055/s-0033-1339129
DOI: 10.1055/s-0033-1339129
paper
Synthesis of 3-exo-Aroylhexahydroindoles via Sequential Gold(I)-Catalyzed Claisen-Type Rearrangement–Epimerization Reactions of cis-4-[N-Tosyl-N-(3-arylprop-2-ynyl)amino]cyclohex-2-en-1-ols
Further Information
Publication History
Received: 18 March 2014
Accepted after revision: 22 April 2014
Publication Date:
02 June 2014 (online)
Abstract
A two-step process for the synthesis of 3-exo-aroylhexahydroindoles is described. cis-4-[N-Tosyl-N-(3-arylprop-2-ynyl)amino]cyclohex-2-en-1-ols were cycloisomerized with a catalytic amount of chloro(triphenylphosphine)gold(I)/silver(I) hexafluoroantimonate (AuPPh3Cl/AgSbF6); subsequent base treatment of the crude mixture provided 3-exo-aroylhexahydroindoles in good yields and complete stereoselectivity. A key step involving a 9-endo-dig attack of the hydroxyl group onto the gold-activated alkyne is proposed. The resulting allyl vinyl ether intermediate underwent a gold-assisted [3,3]-sigmatropic rearrangement to form 3-exo-3-aroylhexahydroindole derivatives.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000084, including complete experimental procedures, analytical data, NMR spectra, and X-ray diffraction analyses.
- Supporting Information
-
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