書誌事項
- タイトル別名
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- Highly Stereoselective Construction of Acyclic Systems by the Reaction of Allyl and Allenyltitanocenes with Ketones
- アリル ・ プロパルギルチタノセン ト ケトン ノ ハンノウ ニ ヨル サジョウ カゴウブツ ノ コウリッタイ センタクテキ コウチク
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抄録
Highly diastereoselective preparation of tert-homoallylic alcohols using organotitanium reagents is described. The reaction of allyltitanocenes, generated by the reductive titanation of allylic sulfides with titanocene(II)-1-butene complex, with phenyl and sterically hindered alkyl methyl ketones produced anti-tertiary homoallylic alcohols with complete diastereoselectivity. Even when sterically less congested alkyl methyl ketones such as methyl ethyl ketone and cyclic enones were employed, the homoallylic alcohols were obtained with unprecedented high diastereoselectivity. Using α-silyl allyl sulfides, β,δ-disubstituted tertiary homoallylic alcohols were obtained with high regio- and stereoselectivity. A range of syn-tertiary homoallylic alcohols were also obtained by the reaction of α-silylallenyltitanocenes generated by the reductive titanation of γ-silylpropargylic carbonates with titanocene(II)-triethyl phosphite complex, with ketones and following desilylation and partial hydrogenation. The construction of three consecutive stereogenic centers has been achieved by two approaches, the addition of allyltitanium reagents to α-chiral ketones and the reaction of ketones with chiral allyltitanocenes generated by the desulfurizative titanation of allylic sulfides obtained by the alkylation of allyl sulfide with secondary halides. Acyclic systems bearing adjacent two quaternary centers were also constructed by the use of allyltitanocenes, generated by the desulfurizative titanation of γ,γ-disubstituted allyl sulfides.
収録刊行物
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- 有機合成化学協会誌
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有機合成化学協会誌 71 (2), 98-108, 2013
公益社団法人 有機合成化学協会
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詳細情報 詳細情報について
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- CRID
- 1390001205340423680
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- NII論文ID
- 10031148202
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- NII書誌ID
- AN0024521X
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- COI
- 1:CAS:528:DC%2BC3sXjsFGjsr8%3D
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- ISSN
- 18836526
- 00379980
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- NDL書誌ID
- 024278210
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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
- Crossref
- CiNii Articles
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- 抄録ライセンスフラグ
- 使用不可