At the advent of cross-coupling chemistry, carbon electrophiles based on halides or psuedohalides were the only suitable electrophilic coupling partners. Almost two decades passed before the first cross-coupling reaction of heteroatom-based electrophiles was reported. Early work by Murai and Tanaka initiated investigations into silicon electrophiles. Narasaka and Johnson pioneered the way in the use of nitrogen electrophiles; while Suginome began the exploration of boron electrophiles. The chemistry reviewed within provides prospective on the use of heteroatomic electrophiles specifically silicon-, nitrogen-, boron-, oxygen-and phosphorus-based electrophiles in transitionmetal catalyzed cross-coupling. For the purposes of this review, a loose definition of crosscoupling is utilized; all reactions minimally proceed via an oxidative addition event. Although not cross-coupling in a traditional sense, we have also included catalyzed reactions that join a heteroatomic electrophile with an in situ generated nu-cleophile. However, for brevity, those involving hydroamination or C-H activation as a key step are largely excluded. This work includes primary references published up to and including October 2018.

The asymmetric Pd-catalyzed decarboxylative allylic alkylation of differentially N-protected piperazin-2-ones allows for the synthesis of a variety of highly enantioenriched tertiary piperazine-2-ones. Deprotection and reduction affords the corresponding tertiary piperazines, which can be employed for the synthesis of medicinally important analogs. The introduction of these chiral tertiary piperazines resulted in imatinib analogs that exhibited comparable antiproliferative activity to that of their corresponding imatinib counterparts.

Fort he first time,a na za-Heckc yclization that allows the preparation of indoline scaffolds is described. Using N-hydroxy anilines as electrophiles,w hich can be easily accessed from the corresponding nitroarenes,t his method provides indolines bearing pendant functionality and complex ring topologies.S ynthesis of challenging indolines,s uch as those bearing fully substituted carbon atoms at C2, is also possible using this method.

Supporting information for this article is given via a link at the end of the document.

Supporting information for this article is given via a link at the end of the document.