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Synlett 2022; 33(14): 1312-1316
DOI: 10.1055/a-1778-8143
cluster
Organic Chemistry in Thailand

4b-Aryltetrahydroindeno[1,2-a]indenes by Acid-Catalyzed Trans­annular Cyclization of Benzannulated Cyclooctene Alcohols

Poramate Songthammawat
a   Laboratory of Medicinal Chemistry, Chulabhorn Research Institute, 54 Kamphaeng Phet 6 Road, Laksi, Bangkok, 10210, Thailand
,
Tanawat Phumjan
a   Laboratory of Medicinal Chemistry, Chulabhorn Research Institute, 54 Kamphaeng Phet 6 Road, Laksi, Bangkok, 10210, Thailand
,
Somsak Ruchirawat
a   Laboratory of Medicinal Chemistry, Chulabhorn Research Institute, 54 Kamphaeng Phet 6 Road, Laksi, Bangkok, 10210, Thailand
b   Program in Chemical Sciences, Chulabhorn Graduate Institute, Chulabhorn Royal Academy, 906 Kamphaeng Phet 6 Road, Laksi, Bangkok, 10210, Thailand
c   Center of Excellence on Environmental Health and Toxicology, Office of the Permanent Secretary (OPS), Ministry of Higher Education, Science, Research and Innovation (MHESI), Bangkok, 10400, Thailand
,
Poonsakdi Ploypradith∗
a   Laboratory of Medicinal Chemistry, Chulabhorn Research Institute, 54 Kamphaeng Phet 6 Road, Laksi, Bangkok, 10210, Thailand
b   Program in Chemical Sciences, Chulabhorn Graduate Institute, Chulabhorn Royal Academy, 906 Kamphaeng Phet 6 Road, Laksi, Bangkok, 10210, Thailand
c   Center of Excellence on Environmental Health and Toxicology, Office of the Permanent Secretary (OPS), Ministry of Higher Education, Science, Research and Innovation (MHESI), Bangkok, 10400, Thailand
› Author AffiliationsThis research project is supported by Thailand Science Research and Innovation (TSRI; DBG6080007 for P.P.), TSRI-Chulabhorn Research Institute (Grant No. 2536703/42320), TSRI-Chulabhorn Graduate Institute, Chulabhorn Royal Academy (FRB650039/0240 Project Code 165423), and a grant from the Center of Excellence on Environmental Health and Toxicology (EHT), OPS, Ministry of Higher Education, Science, Research and Innovation (MHESI).
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Dedicated to the late Professor Robert H. Grubbs

Abstract

By starting from two simple building blocks, benzannulated cyclooctenones were obtained in three steps. Subsequent Grignard/aryl lithium addition to the ketone yielded the corresponding tertiary alcohols that underwent stereoselective acid-catalyzed transannular cyclization to provide a cis-fused 5/5 bicyclic indanylindane framework exclusively. Subsequent stereoselective nucleophilic addition to the indanyl cation by hydride, water, or electron-rich aromatics furnished the 4b-aryltetrahydroindano[1,2-a]indenes in good to excellent yields (up to 92%) in the trans-C9–C9a form in up to a >99:1 diastereomeric ratio.

Key words

carbocations - cyclization - diastereoselectivity - metathesis - acid catalysis - indenoindenes

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1778-8143.
  • Supporting Information


Publication History

Received: 22 January 2022

Accepted after revision: 22 February 2022

Accepted Manuscript online:
22 February 2022

Article published online:
28 April 2022

© 2022. Thieme. All rights reserved

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