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Synlett 2023; 34(04): 359-363
DOI: 10.1055/a-1992-6707
DOI: 10.1055/a-1992-6707
letter
Chemoselective Strain Release of Bicyclo[1.1.1]pent-1-yl Alcohols
We 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.
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 - enonesSupporting 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
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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).