Secondary benzylic alcohols (SBAs) and diarylmethanols (DAMs) are common structural motifs of biologically active and medicinally relevant compounds. Here we report their enantioselective synthesis by -arylation of primary aliphatic and benzylic alcohols under sequential catalysis integrating a Ru-catalyzed hydrogen-transfer oxidation and a Ru-catalyzed nucleophilic addition. The method is applicable to various alcohols and aryl nucleophiles tolerating a range of functional groups, including secondary alcohols, ketones, alkenes, esters, NH-amides, tertiary amines, aryl halides, and heterocycles.Secondary benzylic alcohols (SBAs) and diarylmethanols (DA Ms) constitute valuable synthetic intermediates and prevalent structural motifs of numerous natural products and bioactive compounds. 1,2 Therefore, protocols for their stereoselective synthesis from various accessible starting materials have attracted much attention over the years. Common approaches include potent asymmetric (transfer) hydrogenation of ketones 1,3,4 or 1,2-addition of aryl nucleophiles to aldehydes, 5,6 particularly useful for fine-chemical synthesis when such starting materials are available and do not require additional synthetic steps.Because aliphatic alcohols represent a class of abundant starting materials, increasing attention has been devoted to developing methods for their valorization through selective C−H bond functionalization. [7][8][9] In the context of SBAs, an elegant strategy for the enantioselective alkylation of -C−H bonds of primary benzylic alcohols with unsaturated hydrocarbons (e.g., dienes, enynes) was devised by Krische and co-workers (Scheme 1a). 10,11 The methods of the arylation of -C−H bonds of aliphatic alcohols in the Minisci-type reactions were also established. [12][13][14][15][16][17] (Scheme 1b). Unfortunately, these methods lead to racemic products, leaving the enantioselective -C−H arylation of alcohols unexplored.We have recently reported an enantioselective synthesis of SBAs from unsaturated alcohols and aryl boronic acids under sequential catalysis (Scheme 1c). 18 The one-pot sequence of an Ir-catalyzed isomerization of the starting material and a Ru-catalyzed nucleophilic addition of an aryl boronic acid to the aldehyde intermediate provided a convenient synthetic method with a broad scope and functional group tolerance.

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Reactions of enynones with arenes in TfOH-Py or with zeolite HUSY lead to products of hydroarylation of the acetylene bond.

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