| ○種別 (必須): | □ | 学術論文 (審査論文)
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| ○言語 (必須): | □ | 英語
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| ○審査 (推奨): | □ | Peer Review
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| ○カテゴリ (推奨): | □ | 研究
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| ○共著種別 (推奨): | □ | 国内共著 (徳島大学内研究者と国内(学外)研究者との共同研究 (国外研究者を含まない))
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| ○学究種別 (推奨): |
| ○組織 (推奨): |
| ○著者 (必須): | 1. | (英) Kamikawa, Ken (日) (読)
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| 2. | (英) Tseng, Ya-Yi (日) (読)
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| 3. | (英) Jian Jia-Hong (日) (読)
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| 4. | (英) Takahashi Tamotsu (日) (読)
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| 5. | 小笠原 正道 ([徳島大学.大学院社会産業理工学研究部.理工学域.自然科学系.化学分野]/[徳島大学.理工学部.理工学科.自然科学コース.化学講座])
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| ○題名 (必須): | □ | (英) Planar-Chiral Phosphine-Olefin Ligands Exploiting a (Cyclopentadienyl)manganese(I) Scaffold to Achieve High Robustness and High Enantioselectivity (日)
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| ○要約 (任意): | □ | (英) A series of 2-methyl-1,3-propenylene-bridged (η(5)-diarylphosphinocyclopentadienyl)(phosphine)manganese(I) dicarbonyl complexes 2 have been developed as a new class of phosphine-olefin ligands based on a planar-chiral transition-metal scaffold, which show better robustness as well as higher enantioselectivity over phosphine-olefin ligands 1 with a planar-chiral (η(6)-arene)chromium(0) framework. The practical enantiospecific and scalable synthesis of 2 has been established. Phosphine-olefin ligands 2 enable construction of an effective chiral environment around a transition-metal center upon coordination, and thus their rhodium(I) complexes exhibit excellent catalytic performance in the various asymmetric addition reactions of arylboron nucleophiles. Complex 2b, which has a bis(3,5-dimethylphenyl)phosphino group on the cyclopentadienyl ring, is found to be a superior chiral ligand in the rhodium-catalyzed asymmetric 1,4-addition reactions of arylboronic acids to various cyclic/acyclic enones giving the corresponding arylation products in over 99% ee. On the other hand, 2c and 2d, which have bis[3,5-bis(trifluoromethyl)phenyl]phosphino and bis(3,5-di-tert-buthyl-4-methoxyphenyl)phosphino groups, respectively, are highly efficient chiral ligands in the rhodium-catalyzed asymmetric 1,2-addition reactions of the arylboron nucleophiles to imines or aldehydes showing up to 99.9% ee. The X-ray crystallographic studies of (R)-2b and [RhCl((S*)-2b)]2 reveal the absolute configuration of 2b and its phosphine-olefin bidentate coordination to a rhodium(I) cation. Structural comparison with [RhCl((R*)-1b)]2 postulates the origins of the higher enantioselectivity of newly developed phosphine-olefin ligands 2. (日)
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| ○キーワード (推奨): |
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| ○誌名 (必須): | □ | Journal of the American Chemical Society ([アメリカ化学会])
(pISSN: 0002-7863, eISSN: 1520-5126)
| ○ISSN (任意): | □ | 1520-5126
ISSN: 0002-7863
(pISSN: 0002-7863, eISSN: 1520-5126) Title: Journal of the American Chemical SocietyTitle(ISO): J Am Chem SocPublisher: American Chemical Society (NLM Catalog)
(Scopus)
(CrossRef)
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| ○巻 (必須): | □ | 139
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| ○号 (必須): | □ |
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| ○頁 (必須): | □ | 1545 1553
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| ○都市 (任意): |
| ○年月日 (必須): | □ | 西暦 2017年 1月 19日 (平成 29年 1月 19日)
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| ○URL (任意): |
| ○DOI (任意): | □ | 10.1021/jacs.6b11243 (→Scopusで検索)
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| ○PMID (任意): | □ | 28045511 (→Scopusで検索)
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| ○WOS : | □ | 000393355600037
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| ○機関リポジトリ : | □ | 113018
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| ○備考 (任意): | 1. | (英) Article.ELocationID: 10.1021/jacs.6b11243 (日)
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| 2. | (英) Article.PublicationTypeList.PublicationType: Journal Article (日)
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