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Enantioselective Additions of Aryltitanium Tris(isopropoxide) to Ketones: Structure of [( i‐ PrO) 2 Ti{μ‐( S )‐BINOLate}(μ‐O‐ i‐ Pr)TiPh(O‐ i‐ Pr) 2 ], Study of Mechanistic and Stereochemical Insights
Author(s) -
Wu KuoHui,
Kuo YiYin,
Chen ChienAn,
Huang YiLing,
Gau HanMou
Publication year - 2013
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201200672
Subject(s) - chemistry , enantioselective synthesis , reagent , aryl , nucleophile , ligand (biochemistry) , tris , medicinal chemistry , group 2 organometallic chemistry , organic chemistry , stereochemistry , molecule , catalysis , biochemistry , alkyl , receptor
Aryl addition reactions of ArTi(O‐ i‐ Pr) 3 to aromatic, heteroaromatic, or α,β‐unsaturated ketones are described, producing tertiary alcohols in good to excellent enantioselectivities of up to 97% ee . The structure of the dititanium complex [( i‐ PrO) 2 Ti{μ‐( S )‐BINOLate}(μ‐O‐ i‐ Pr)TiPh(O‐ i‐ Pr) 2 ] [( S )‐ 4 ] that simultaneously bears a chiral directing ligand and a nucleophile is reported. Complex ( S )‐ 4 possesses a pocket structure and has been illustrated as the key active species for addition reactions of both aldehydes and ketones. Mechanistic and stereochemical insights concerning addition reactions of organometallic reagents to organic carbonyls are rationalized based on the pocket structure and pocket size of ( S )‐ 4 .