書誌事項
- タイトル別名
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- Catalytic Enantioselective Synthesis of Novel Atropisomeric Compounds having an N-C Chiral Axis and Their Application to Asymmetric Reaction
- 炭素-窒素不斉軸を有する新規アトロプ異性化合物の触媒的不斉合成と不斉反応への応用
- タンソ チッソ フセイジク オ ユウスル シンキ アトロプ イセイ カゴウブツ ノ ショクバイテキ フセイ ゴウセイ ト フセイ ハンノウ エ ノ オウヨウ
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Atropisomeric compounds due to rotational restriction around an N-C bond have received much attention recently as novel chiral molecules. However, catalytic enantioselective synthesis of such N-C axially chiral compounds has not so far been reported. We succeeded in the highly enantioselective syntheses of atropisomeric ortho-tert-butyl anilides, lactams and indoles having an N-C chiral axis through chiral palladium-catalyzed N-C bond forming reactions.<br>That is, in the presence of (R)-DTBM-SEGPHOS-Pd(OAc)2 catalyst, N-arylation (Buchwald-Hartwig amination) of achiral ortho-tert-butylanilides with p-iodonitrobenzene proceeded in a highly enantioselective manner (88−96% ee) to give atropisomeric N-(p-nitrophenyl)anilides in good yields. The application of the present catalytic enantioselective N-arylation to an intramolecular version gave atropisomeric lactam derivatives with high optical purity (92−98% ee). The α-alkylation with the lithium enolate prepared from the atropisomeric anilide and lactam products with various alkyl halides proceeded with high diastereoselectivity (diastereomer ratio=31:1-80:1).<br>On the other hand, 5-endo-hydroaminocyclization of achiral ortho-alkynylanilines using (R)-SEGPHOS-PdCl2 catalyst afforded optically active atropisomeric indole derivatives (up to 83% ee) in good yields.
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 69 (9), 985-993, 2011
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
- 1390001205339543296
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- NII論文ID
- 10029617906
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- NII書誌ID
- AN0024521X
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- COI
- 1:CAS:528:DC%2BC3MXhtFyltr%2FP
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- ISSN
- 18836526
- 00379980
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- NDL書誌ID
- 11230312
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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
- KAKEN
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- 抄録ライセンスフラグ
- 使用不可
