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Synlett 2015; 26(19): 2685-2689
DOI: 10.1055/s-0035-1560590
DOI: 10.1055/s-0035-1560590
letter
Synthesis of Silylcyclopropanes through the Catalytic Generation of Zinc Silylcarbenoids from Enynones
Weitere Informationen
Publikationsverlauf
Received: 03. Juli 2015
Accepted after revision: 21. Oktober 2015
Publikationsdatum:
06. November 2015 (online)
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Dedicated to Professor Antonio Echavarren on the occasion of his 60th birthday
Abstract
A simple methodology for the preparation of 1-furyl-1-(silyl)cyclopropanes is reported. ZnCl2 serves as inexpensive, low-toxicity catalyst for the generation of silylcarbenes from enynones, which can be trapped by alkenes under mild reaction conditions. These cyclopropanations take place in high yields and selectivities, showing a remarkable scope.
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560590.
- Supporting Information
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References and Notes
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- 16 Representative Procedure: To a solution of enynone 1 (0.30 mmol) and alkene 2 (1.8 mmol, 6.0 equiv) in 1,2-dichloroethane (3.0 mL, 0.10 M), ZnCl2 (4.0 mg, 10 mol%) was added at ambient temperature. The Schlenk flask was placed in a preheated oil bath at 50 °C and the reaction mixture was stirred until consumption of 1 (TLC analysis). After elimination of the solvent, purification by flash column chromatography (SiO2, hexane–EtOAc) afforded the corresponding cyclopropanes 3. Characterization data for compound 3a: 1H NMR (300 MHz, CDCl3): δ = 7.05–7.23 (m, 3 H), 6.92–7.03 (m, 2 H), 5.86 (s, 1 H), 2.37 (s, 3 H), 2.34 (dd, J = 7.9, 6.1 Hz, 1 H), 2.25 (s, 3 H), 1.63 (dd, J = 6.0, 4.8 Hz, 1 H), 1.39 (dd, J = 7.8, 4.8 Hz, 1 H), 0.09 (s, 9 H). 13C NMR (75 MHz, CDCl3): δ = 194.4 (C), 156.6 (C), 153.9 (C), 138.3 (C), 127.9 (CH), 127.6 (CH), 125.9 (CH), 121.6 (C), 107.5 (CH), 29.0 (Me), 26.9 (CH), 17.7 (C), 15.1 (CH2), 14.2 (Me), –2.9 (Me). HRMS (ESI): m/z [M]+ calcd for C19H24O2Si: 312.1546; found: 312.1543.
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- 23 Unfortunately, attempts to obtain cyclopropanols by Tamao–Fleming oxidation (on compounds 3w–x) through various standard procedures failed, leading to complex mixtures or hydrodesilylation product. Various attempts to perform Hiyama couplings were also unsuccessful.
For using Simmons–Smith-type carbenoids, see:
Low yields were commonly obtained due to steric hindrance. Improvements by using alkenes bearing an oxygen-directing group were described, see:
For representative examples using metal carbenoids derived from diazo compounds, see:
For the preparation of (TMS)phosphinocarbenes, see:
For representative examples dealing with the generation of furylcarbenes from enynones with other metals, see:
For related silicon-to-carbon migrations of phenyl groups, see: