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The ligand (<jats:italic>R<\/jats:italic>)\u2010<jats:bold>1<\/jats:bold>, which lacks <jats:italic>C<\/jats:italic><jats:sub>2<\/jats:sub>\u2010symmetry and flexible linkers, in combination with Ti(O<jats:italic>i<\/jats:italic>Pr)<jats:sub>4<\/jats:sub>, has been demonstrated to promote the enantioselective cyanation of aldehydes with trimethylsilylcyanide (TMSCN), giving excellent enantioselectivities of up to 98\u2009% <jats:italic>ee<\/jats:italic> and high yields of up to 99\u2009%. The use of this bifunctional catalytic system obviates the need for additives and is extremely simple as the reagents are added in one portion at the beginning of the reaction. The protocol has been found to tolerate a relatively wide range of aldehydes when 10\u2005mol\u2009% of the (<jats:italic>R<\/jats:italic>)\u2010<jats:bold>1<\/jats:bold>\/Ti(O<jats:italic>i<\/jats:italic>Pr)<jats:sub>4<\/jats:sub> complex is deployed in CH<jats:sub>2<\/jats:sub>Cl<jats:sub>2<\/jats:sub> at \u221240\u2009\u00b0C, the conditions which proved most practical and effective. The asymmetric cyanations also proceeded with lower catalyst loadings (5\u2005mol\u2009%, or even 2\u2005mol\u2009%), still giving satisfactory enantiomeric excesses and yields. Interestingly, the use of freshly distilled TMSCN dried over CaH<jats:sub>2<\/jats:sub> gave a low enantioselectivity and only a moderate yield of the adduct as compared with direct use of the commercial reagent. The results of <jats:sup>13<\/jats:sup>C\u2005NMR spectroscopic studies implicate HCN as the actual reactive nucleophile.<\/jats:p>","DOI":"10.1002\/chem.200701660","type":"journal-article","created":{"date-parts":[[2008,1,9]],"date-time":"2008-01-09T14:17:55Z","timestamp":1199888275000},"page":"2223-2231","source":"Crossref","is-referenced-by-count":51,"title":["A New Strategy for Designing Non\u2010<i>C<\/i><sub>2<\/sub>\u2010Symmetric Monometallic Bifunctional Catalysts and Their Application in Enantioselective Cyanation of 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