Asymmetric borylation of N-tert-butanesulfinyl alimine with bis(pinacolato)diboron gives alpha-amino boronate ester following cleavage of N-S bond.

Rhodium catalyzed enantioselective synthesis of 3,3-disubstituted 1-indanone is described. The mechanism is believed to occur by transmetalation of rhodium species by aryldiolborate, insertion into the alkyne to generate alkenyl rhodium species, then subsequent 1,4-rhodium migration to give aryl rhodium, then intramolecular insertion into the tethered enone generates oxa-pi-allyl rhodium species. This, upon trasmetalation with arylboronate, releases the boron enolate, which following hydrolysis affords the chiral 3,3-disubstituted 1-indanone.

Treatment of N-Boc pyrrolidine or O-alkyl carbamate with s-BuLi and (-)-sparteine generates their respective enantiopure carbanions. The carbanion of O-alkyl carbamate can be quenched with phenyl boronate ester, which then undergoes 1,2-metalate rearrangement to generate, upon oxidative hydrolysis of the boronate, enantiopure carbamate/alcohol. The carbanion of N-Boc pyrrolidine can be transmetalated to organozinc species to undergo palladium-mediated negishi coupling with aryl halide to afford enantiopure, 2-aryl N-Boc pyrrolidine.

Halovinyl-N-methyliminodiacetate boronate is a useful intermediate that can be used in Stille, Heck, Suzuki-Miyaura, and Nigishi couplings to sterospecifically extend its conjugated unsaturated systems. Its air-stability is a plus and also under mild basic conditions, MIDA ligand can be removed to reveal a sp2-hybridized boron, which can react via sm to cross-couple with other partners.

Oxidative Heck coupling of arylboronate with vinyl ether, enamide, and enone to generate substituted ketone, enamide and enone. Note the preference of sterics that determine the regioselective outcome.

In-situ formation of aryl-boronate at the meta position, followed by bromination or chlorination with CuBr2/CuCl2. Note the meta-regioselectivity.

1,2-addition of aryl, heteroaryl, alkenylboronic acids to aromatic, heteroaromatic, and aliphatic aldehydes is effected in the presence of palladium with thioether-imidazolium chloride ligand, in good-excellent yields.

Michael addition of acrylate esters by arylboronic acid effects hydroarylation. It is postulated that the presence of bulky phosphine ligands crowds the metal center, thereby preventing beta-hydride elimination. Therefore, Mizoroki-Heck-type oxidation is prevented. Water may also be accelerating this process. Lastly, exposure to air seems to oxidize Pd(O) to Pd(II), reactivating the catalytic system.

Various aliphatic aldehyde-derived hyrazones are allylated with a catalytic amount of indium (I) and allylborate to generate hydrazides. Alpha-beta unsaturated hydrazone gives 1,2-addition product exclusively. Methanol is noted to play an important role in converting allylborate with indium iodide into catalytically active species.