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Synlett 2023; 34(04): 359-363
DOI: 10.1055/a-1992-6707
letter

Chemoselective Strain Release of Bicyclo[1.1.1]pent-1-yl Alcohols

Yue Ma
a   Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian, 116024, P. R. of China
,
Yinan Ai
a   Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian, 116024, P. R. of China
,
Songjie Yu∗
a   Zhang Dayu School of Chemistry, Dalian University of Technology, Dalian, 116024, P. R. of China
b   Institute of Molecular Science and Engineering, Institute of Frontier and Interdisciplinary Sciences, Shandong University, Qingdao, 266237, P. R. of China
› Author AffiliationsWe thank the Dalian University of Technology, the Fundamental Research Funds for the Central Universities, and the Shandong Non-metallic Materials Institute for financial support. S.Y. thanks the Taishan Scholar of Shandong Province and the Qilu Young Scholar of Shandong University for funding.
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In memory of Professor Keli Han.

Abstract

The chemoselective C–C bond cleavage of bicyclo[1.1.1]pent-1-yl alcohols (BCP-OHs) was examined. Highly ring-strained BCP-OHs were found to be particularly reactive, delivering cyclobutanone derivatives through a base-mediated single C–C bond cleavage or α,β-unsaturated ketones by palladium-catalyzed dual C–C bond cleavage.

Key words

bicyclopentyl alcohols - strain release - C–C bond cleavage - chemoselectivity - cyclobutanones - enones

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1992-6707.
  • Supporting Information


Publication History

Received: 01 October 2022

Accepted after revision: 04 December 2022

Accepted Manuscript online:
04 December 2022

Article published online:
03 January 2023

© 2022. Thieme. All rights reserved

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  • 17 Cyclobutanones 2a–o; General Procedure A dried 8 mL vial was charged with the appropriate BCP-OH 1 (0.1 mmol), Cs2CO3 (30 mol%, 9.8 mg), and anhyd THF (1 mL). The vial was then sealed with a cap and the mixture was stirred at 100 ℃ for 16 h. The mixture was then purified by flash column chromatography [silica gel, PE–EtOAc (60:1)]. The TLC plate for the product was visualized with phosphomolybdic acid stain. 3-Methyl-3-(2-tolyl)cyclobutan-1-one Colorless oil; yield: 17.2 mg (99%). 1H NMR (400 MHz, CDCl3): δ = 7.22–7.13 (m, 4 H), 3.60–3.48 (m, 2 H), 3.20–3.04 (m, 2 H), 2.37 (s, 3 H), 1.58 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 207.1, 145.5, 135.2, 131.7, 126.9, 126.6, 126.3, 59.2, 34.7, 28.6, 20.4. GC/MS (EI): m/z [M+] calcd for C12H14O: 174.1; found: 174.1. α,β-Unsaturated Ketones 3a–f; General Procedure A dried 8 mL vial was charged with the appropriate BCP-OH 1 (0.1 mmol), Cs2CO3 (30 mol%, 9.8 mg), Pd(OAc)2 (5 mol%, 1.2 mg), and anhyd THF (1 mL). The vial was then sealed with a cap and the mixture was stirred at 100 ℃ for 16 h. The mixture was then purified by flash column chromatography [silica gel, PE–EtOAc (20:1)]. The TLC plate for the product was visualized with phosphomolybdic acid stain. (3E)-4-Phenylpent-3-en-2-one Colorless oil; yield: 15.5 mg (97%). 1H NMR (400 MHz, CDCl3): δ = 7.53–7.36 (m, 5 H), 6.53 (s, 1 H), 2.56 (s, 3 H), 2.32 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 198.9, 153.9, 142.6, 129.1, 128.6, 126.5, 124.6, 32.2, 18.4. GC/MS (EI): m/z [M+] calcd for C11H12O: 160.1; found: 160.1.
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