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

Yue Ma; Yinan Ai; Songjie Yu

doi:10.1055/a-1992-6707

Synlett, Table of Contents

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

^aZhang Dayu School of Chemistry, Dalian University of Technology, Dalian, 116024, P. R. of China

,

Yinan Ai

^aZhang Dayu School of Chemistry, Dalian University of Technology, Dalian, 116024, P. R. of China

,

Songjie Yu∗

^aZhang Dayu School of Chemistry, Dalian University of Technology, Dalian, 116024, P. R. of China

^bInstitute of Molecular Science and Engineering, Institute of Frontier and Interdisciplinary Sciences, Shandong University, Qingdao, 266237, P. R. of China

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Abstract

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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

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References

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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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21 Analysis of Cs₂CO₃ by inductively coupled plasma atomic-emission spectroscopy showed the presence of low levels of transition-metal residues; for example, Pd < 0.04 mg/L, Cu < 0.01 mg/L, Co < 0.007 mg/L, Ni < 0.015 mg/L (for details, see the Supporting Information).

Supplementary Material

Supporting Information