Rediscovering Organocopper Chemistry Through Copper Hydride. It’s All About the Ligand

Abstract

A personalized account is presented that reveals the real stories behind the development of copper hydride chemistry at UCSB over the past decade: names, events, and the thinking behind the discoveries. Both achirally ligated and nonracemically complexed copper hydride reagents are discussed within the context of the field as a whole.

Reduction of Aromatic and Aliphatic Esters Using the Reducing Systems MoO2(acac)2 or V(O)(OiPr)3 in Combination with 1,1,3,3‐Tetramethyldisiloxane

“…When the reactions were performed with [Co(acac) 3 plex (Table 1, entry 10). Further studies with PMHS were not pursued because of the formation of gels, [45] which complicated the clean isolation of the alcohol. TMDS was therefore used as the hydride source.…”

ChemInform Abstract: Designer‐Surfactant‐Enabled Cross‐Couplings in Water at Room Temperature

“…66 Although the reagent is stable to water and, in fact, was used long ago by Stryker to enhance the rate of quenching of copper(I) intermediates (e.g., enolates resulting from 1,4 addition of hydride from (Ph 3 P)CuH, 67 its use in a strictly aqueous medium is not among the available protocols. It might even be argued that water as “solvent” presents a likely major (Ref.65) (Ref.…”

1,2-Bis(diphenylphosphino)benzene

“…35 This procedure was applied to the one-pot reduction of ketones with CuH generated in situ and triethylsilane to achieve the hydrosilylation of ketones in very high yield. 36 Dppben, BIPHEP, and SEGPHOS were suitable ligands for this transformation.…”

“…12 This new reagent, named as (BDP)CuH, is generated in situ (eq 15), leading to high turnover numbers and is more reactive than the parent compound. 12, 35 It tolerates ketone, ester, and nitrile groups, and reduces not only conjugated double bonds but also acetylenic esters with typical 90-96% yields. Reaction times, usually 2-6 h, can be shortened by using microwave irradiation.…”