BINOL catalysis substitution

Terminal alkynes such as 4-phenylbutyne undergo nickel(II)-catalysed reaction with dialkylaluminium hydride to give vinylaluminium reagents (84), which react with aldehydes to give enantioselective formation of a-substituted secondary allylic alcohols, via Hg-BINOL catalysis. The vinylaluminium alkyl groups are chosen in such away that the reagent does not just directly reduce the aldehyde. 

Very recently, Fan et al. [13] reported on the use of a water-soluble PEO-substitut-ed first- and second-generation Frechet-type dendrimer with a chiral BINOL (1,1 -bi-2-naphthol) unit in catalysis. The enantiomeric excess in asymmetric hydrogenation of 2-[p-(2-methylpropyl)phenyl]acrylic acid with [RuCl(BINAP)(cymene)]Cl in an aqueous system was reported to increase upon addition of the dendritic... 

Recently, chiral anion catalysis has been introduced as a useful strategy in metal-catalyzed asymmetric transformations. You and co-workers disclosed that chiral substituted binol phosphate could serve as a suitable counteranion in Ag-catalyzed AFC reaction of ortfto-alkynylaryl aldimines 25 with indoles, affording enantioenriched 1,2-dihydroisoquinoline 27 in moderate to good yields and ee (Scheme 6.10). ... 

It was demonstrated that BINOL catalysts authorize the /3- and /-functionalizations of the allyltin reagents without lowering the enantioselectivity level [223], and such a strategy was used in the total syntheses of macrolides [224] or substituted tetrahydropyran units [225]. It was noteworthy that the BINOL-Ti catalysis was extended to the enantioselective allylation of alkyl and aromatic ketones in good yields with up to 96% ee [226]. Silver/BINAP was used as well, with a marked anti selectivity, when using crotyltins whatever is the nature, (E) or (Z) of the double bond [227]. This reaction was extended to other organometallics such as 2,4-pentadienylstannanes [228] or buta-2,3-dienylstannanes [229] (Scheme 6.26). 

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