Abstract
The alkali metal-templated addition of aryloxides across the double bond of non-conjugated cyclopropenes is described. High cis-selectivity is achieved through a directing effect of a strategically positioned carboxamide functionality.
Highlights
Noncatalytic ring-retentive diastereoselective additions of various nucleophilic entities across the double bond of cyclopropenes are much less common;[3] this unorthodox approach towards cyclopropyl-based scaffolds is very attractive from a synthetic standpoint
We rationalized that a stepwise approach involving a directed nucleophilic addition to pre-generated, isolable cyclopropene 12 could potentially be explored as an alternative route
The compound was prepared according to the typical procedure B, employing N,N-diethyl-1-phenylcycloprop-2-ene-1carboxamide (12a)13b (50 mg, 0.232 mmol, 1.00 equiv.) and 4-methoxyphenol (14b) (115 mg, 0.929 mmol, 4.00 equiv.) followed by preparative column chromatography on silica gel to afford the title compound as an inseparable mixture of diastereomers, colorless oil, Rf 0.19
Summary
Ring-retentive metal-catalyzed additions to cyclopropenes en route to stereochemically defined cyclopropanes has evolved into a rapidly growing area during the past decade.[1,2] Noncatalytic ring-retentive diastereoselective additions of various nucleophilic entities across the double bond of cyclopropenes are much less common;[3] this unorthodox approach towards cyclopropyl-based scaffolds is very attractive from a synthetic standpoint. The compound was prepared according to the typical procedure B, employing N,N-diethyl-1-phenylcycloprop-2-ene-1carboxamide (12a)13b (50 mg, 0.232 mmol, 1.00 equiv.) and 4(tert-butyl)phenol (14c) (140 mg, 0.929 mmol, 4.00 equiv.) followed by preparative column chromatography on silica gel to afford the title compound as an inseparable mixture of diastereomers (dr 33 : 1), colorless oil, Rf 0.25 (hexanes/EtOAc 3 : 1).
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