期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 18, 期 7, 页码 1969-1983出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201102426
关键词
asymmetric catalysis; density functional calculations; hydrogen transfer; ruthenium; sulfinylimines
资金
- Spanish Ministerio de Ciencia e Innovacion (MICINN) [CSD2007-00006, CTQ2007-65218, CTQ2011-23336]
- Generalitat Valenciana [PROMETEO/2009/039]
- Spanish Ministerio de Educacion [AP-2008-00989]
A highly efficient Ru catalyst based on an achiral, very simple, and inexpensive amino alcohol ligand (2-amino-2-methylpropan-1-ol) has been developed for the asymmetric transfer hydrogenation (ATH) of chiral N-(tert-butylsulfinyl)imines. This complex is able to catalyze the ATH of both aromatic and the most challenging aliphatic sulfinylimines by using isopropyl alcohol as the hydrogen source. The diastereoselective reduction of aromatic, heteroaromatic, and aliphatic sulfinylketimines, including sterically congested cases, over short reaction times (14 h), followed by desulfinylation of the nitrogen atom, affords the corresponding highly enantiomerically enriched (ee up to >99?%) a-branched primary amines in excellent yields. The same ligand was equally effective for the synthesis of both (R)- and (S)-amines by using the appropriate absolute configuration in the iminic substrate. DFT mechanistic studies show that the hydrogen-transfer process is stepwise. Moreover, the origin of the diastereoselectivity has been rationalized.
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