Palladium-Catalyzed Asymmetric O-1,5-Addition with Oximes via Hydroximation of Unsaturated Esters

Abstract

Different from electronically matched 1,4-and 1,6additions, herein, we disclose an electronically mismatched 1,5conjugate addition process with oximes as the nucleophiles. By this design, the oxime moieties are readily introduced to the γ-position of the electron-deficient substrates in good yields, excellent regioselectivities, and high enantioselectivities. The corresponding allyl oximes are also conveniently transformed into a series of valuable enantioenriched skeletons.

Chemodivergent Tandem Hydroalkylation and Hydroalkenoxylation of Conjugated Enynes

“…Continued with our group’s interest in Pd-catalyzed hydrofunctionalizations, ,, we selected conjugated enyne 1a and ketoester 2a as the substrates. We expected that the formed PdH catalyst might induce a typical hydroalkylation process first to construct an allene intermediate in situ, which then served as the reactant for the following critical hydroalkenoxylation.…”

Stereoselective Synthesis of Polysubstituted Dihydropyrroles via 1,5‐Addition and N‐1,4‐Addition Cascade

“…However, the related transformation involving this 1,5addition model is still rare and waiting for extensive explora-tion. Based on our prior work, [8][9][10] we envisioned that a sequential 1,5-addition and aza-Michael addition might provide a novel route to achieve polysubstituted dihydropyrroles stereoselectively (Scheme 1b). However, the proposal is not straightforward.…”