A versatile synthesis, including asymmetric synthesis, of bicyclo[n.1.0]alkanes from cyclic ketones via the magnesium carbenoid 1,3-CH insertion as a key reaction

作者：Satoh Tsuyoshi^*; Ogata Shingo; Wakasugi Daisuke

来源：Tetrahedron Letters, 2006, 47(40): 7249-7253.

DOI：10.1016/j.tetlet.200607.140

• bicyclo[n.1.0-alkane
• cyclopropane
• sulfoxide-magnesium exchange
• magnesium carbenoid
• C-H insertion

Treatment of 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from various cyclic ketones and chloromethyl p-tolyl sulfoxide in three steps, in high yields, with lithium enolate of tert-butyl acetate or its homologues gave the adducts in quantitative yields. The adducts were treated with isopropylmagnesium chloride in ether in dry toluene as the reaction solvent to afford bicyclo[n.1.0]alkanes in high to quantitative yields via magnesium carbenoid 1,3-CH insertion. When this method was carried out starting from unsymmetrical cyclic ketones and (R)-chloromethyl p-tolyl sulfoxide, an asymmetric synthesis of bicyclo[n.1.0]alkane was realized.

• 出版日期2006-10-2