The advent of C(sp3)–H functionalization has heralded a paradigm shift in natural product synthesis. Indeed, several reports in which C–H functionalization serves as the key step in the synthesis have appeared over the years. The purpose of this Microreview is briefly to summarize total syntheses reported during 2014–2016 with emphasis on the most innovative results relating to C–H functionalization. In addition, new advances in the field of Rh‐ and Pd‐catalyzed C(sp3)–H functionalization are discussed with the aim of providing readers with new disconnection ideas for their total synthesis endeavors.

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The aldol addition of methyl ketones to b-siloxy and a-methyl b-siloxy aldehydes is described. Careful control of mechanistically distinct aldol reactions leverages 1,2-and 1,3-asymmetric induction, selectively forming syn and anti aldol adducts with excellent diastereocontrol. Experimental and theoretical investigations have provided insight to the factors governing diastereoselectivity.

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Scheme 1. Conventional aldol approach to polypropionates.Scheme 2. Synthesis of polypropionates by one-pot aldol cascades using aldehyde-derived super-silyl enol ethers. Si = Si(TMS) 3 . TMS = trimethylsilyl.