Asymmetric Addition of Boron and Silicon Nucleophiles

Activation of the Si–B interelement bond related to catalysis

“…1,2 Since then, important progress has been made as reflected by numerous reviews published in recent years, often covering certain aspects of this chemistry. [3][4][5][6][7][8][9] However, a full treatise of this timely topic such as our initial review is missing. The present Review is an update that completely summarises the literature published from January 2013 to April 2020 following our earlier organization.…”

Nickel-Mediated Enantiospecific Silylation via Benzylic C–OMe Bond Cleavage

“…We were optimistic that the methodology developed by Shi, Jarvo, ,− and others ,, (Scheme a) could be borrowed for the use of Me 3 SiMgI as the coupling partner; however, these literature protocols were not amenable to Me 3 SiMgI, and traces of the cross-coupled product were observed (Scheme c), highlighting the limitation of these literature strategies. The commonly employed silylating agent PhMe 2 SiBpin , also failed to furnish the desired product. As a result, we developed an AgF-assisted nickel catalysis that results in the complete conversion of benzylic methyl ethers.…”

Allylic cross-coupling using aromatic aldehydes as α-alkoxyalkyl anions

“…The reaction of SIPr-ligated CuCl (A), KOt-Bu and a silylboronate produces a silylcopper(I) species B. The 1,2-addition of silylcopper(I) B to the aromatic aldehyde 1 [15][16][17][18][19] and the subsequent [1,2]-Brook rearrangement from the obtained α-silyl-substituted copper(I) alkoxide C forms the key intermediate, an α-silyloxybenzylcopper(I) species D. The transmetallation between D and an allylpalladium(II) species F that is generated through the oxidative addition of an allylic carbonate 2 across a palladium(0)-DPPF complex E, followed by reductive elimination from G produces the homoallylic alcohol 3 and then regenerate A and E for the next catalytic cycle [20][21][22][23].…”