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The hydroacylation reaction is an attractive subfield of C–H bond functionalization reactions, realizing direct transformation of the acyl C–H bond of aldehydes. The asymmetric hydroacylation reactions, either intra- or intermolecular, have been developed in recent years with various catalytic systems, among which the Rh-based catalysts hold a central position. In this chapter, we present recent developments of the asymmetric hydroacylation of alkenes, allenes, alkynes, and ketones.

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