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

Chia-Jung Liang; Xuan-Yi Jiang; Ming-Chang P. Yeh

doi:10.1055/s-0033-1339129

Synthesis, Table of Contents

Synthesis 2014; 46(16): 2220-2224
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

Authors

Chia-Jung Liang

Department of Chemistry, National Taiwan Normal University, 88 Ding-Jou Road, Section 4, Taipei 11677, Taiwan, R. O. C. Fax: +886(2)29324249 Email: cheyeh@ntnu.edu.tw
Xuan-Yi Jiang

Department of Chemistry, National Taiwan Normal University, 88 Ding-Jou Road, Section 4, Taipei 11677, Taiwan, R. O. C. Fax: +886(2)29324249 Email: cheyeh@ntnu.edu.tw
Ming-Chang P. Yeh*

Department of Chemistry, National Taiwan Normal University, 88 Ding-Jou Road, Section 4, Taipei 11677, Taiwan, R. O. C. Fax: +886(2)29324249 Email: cheyeh@ntnu.edu.tw

Abstract

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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.

Key words

alcohols - alkynes - cyclization - ethers - indoles

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References

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