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- 武田 敬
- 広島大学大学院医歯薬学総合研究科
書誌事項
- タイトル別名
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- Development of New Synthetic Reactions Featuring Tandem Carbon-Carbon Bond Formation
- レンゾクテキ タンソ タンソ ケツゴウ ケイセイ ハンノウ オ キジクトスル シンキ ゴウセイ ハンノウ ノ カイハツ ケンキュウ
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Development of new synthetic reactions that feature a tandem process triggered by Brook rearrangement, a C-to-O 1,2-anionic shift of a silyl group, will be discussed. A basic motif for the strategy is the generation of an α-siloxy carbanion by the reaction of acylsilanes with ketone enolates and then trapping the anions by intra- and inter-molecular electrophiles. For example, the reaction of benzoyltrimethylsilane with lithium enolates of methyl ketones produced 1,2-cyclopropanediols via Brook rearrangement of the initial 1,2-adduct and subsequent internal aldol reaction. This concept was applied to the synthesis of five- and seven-membered carbocycles using the reaction of acryloylsilanes with enolates of alkyl and alkenyl methyl ketones, respectively. Furthermore, we found that the use of enolate of 2-cycloheptenone instead of the enolates of alkenyl methyl ketone as the four-carbon unit in the [3+4] annulation produces bicyclo[3.3.2]- decenone derivatives, in which the two-atom internal tether could be cleaved to give the cis-3,4,8-trisubstituted cyclooctenone enol silyl ethers stereoselectively. The α-siloxy carbanions can be also generated by an γ-anion-induced ring cleavage of α,β-epoxysilanes. Thus, O-silyl cyanohydrins of β-silyl-α,β-epoxyaldehyde can function as a highly functionalized homoenolate equivalent via a tandem sequence involving base-promoted ring opening, Brook rearrangement, and alkylation at the allylic position. Based on these results, we developed several new synthetically useful reactions in which three methods for the generation of a carbanion at the γ-position, i.e., deprotonation, reaction of acylsilanes with a nucleophile followed by Brook rearrangement, and a conjugate addition of a nucleophile to an enoate system bearing an epoxysilane moiety at the α-position, were used.<br>
収録刊行物
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- 薬学雑誌
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薬学雑誌 127 (9), 1399-1418, 2007-09-01
公益社団法人 日本薬学会
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詳細情報 詳細情報について
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- CRID
- 1390001206129501312
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- NII論文ID
- 110006380724
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- NII書誌ID
- AN00284903
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- ISSN
- 13475231
- 00316903
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- NDL書誌ID
- 8937165
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- 本文言語コード
- ja
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- データソース種別
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- JaLC
- NDL
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- 使用不可