Highly Stereoselective Construction and Chiral Transfer Ring-expansion of Highly Substituted Cyclopropanes

Nishii Yoshinori

doi:10.5059/yukigoseikyokaishi.73.701

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多置換シクロプロパンの高立体選択的合成と不斉伝搬環拡大反応
タチカンシクロプロパンノコウリッタイセンタクテキゴウセイトフセイデンパンカンカクダイハンノウ

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Description

Highly stereoselective synthesis of multi-substituted cyclopropane is important owing to their distribution in nature, and significant biological activities of their analogs. We report here the highly stereoselective synthesis of multi-functionalized cyclopropanes using the SmI₂-promoted Reformatsky-type reaction, acylation, silylation of 1-chlorocyclopropanecarboxylic esters, and the fundamental Reformatsky reaction of 1-bromocyclopropanecarboxylic esters. As the stereo inductive transformation of synthesized highly substituted cyclopropanes, we describe Lewis acid-mediated ring-expansion of methyl (arylhydroxymethyl)-cyclopropanecarboxylates to afford 1,2-dihydronaphthalene-3-carboxylic acid esters. In addition, total syntheses of (+/−)-cyclogalgravin, its dicarboxyl analog, and three kinds of (+)-podophyllic aldehydes have been achieved. Key steps include highly stereoselective constructions of tetra-substituted cyclopropanes and the Lewis acid-mediated chiral transfer ring expansion with excellent level of stereoinductions.

Journal

Journal of Synthetic Organic Chemistry, Japan

Journal of Synthetic Organic Chemistry, Japan 73 (7), 701-712, 2015

The Society of Synthetic Organic Chemistry, Japan

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