Rhodium-catalysed substitutive arylation of cis-allylic diols with arylboroxines

Abstract

Substitutive arylation of cis-allylic diols occurs upon treatment with arylboroxines in the presence of a rhodium(I) catalyst; the reaction proceeds through the addition of an intermediate arylrhodium(I) species across the carbon-carbon double bond and subsequent beta-oxygen elimination.

Chiral Olefins as Steering Ligands in Asymmetric Catalysis

“…[97] Under the reaction conditions, the readily formed cyclic arylboronic esters 167 serve as acceptors for a syn-1,2-carborhodation to give 168. A subsequent b-oxygen elimination regenerates the rhodium catalyst and releases the optically active alcohols 166.…”

Rhodium‐ and Palladium‐Catalyzed Asymmetric Conjugate Additions

“…Krische and coworkers reported the intramolecular trapping of a chiral Rh-enolate by an electrophile [212]. The ECA of phenylboronic acid onto an α,β-unsaturated ketone having a pendant ketone (164) results in the formation of an (oxa-π-allyl)rhodium species, which subsequently undergoes an intramolecular aldol addition onto the ketone fragment. Because of the close proximity of the electrophile, the reaction is kinetically favored and protic conditions can be used.…”

Rh-catalyzed asymmetric 1,4-addition reactions to α,β-unsaturated carbonyl and related compounds: an update

“…Based on this transformation, the first stereoselective total synthesis of cherylline was disclosed. [205][206][207][208][209][210][211][212] An efficient (S/C, substrate/catalyst, up to 500) Rh-catalyzed addition of diverse arylboronic acids 2 to 2-nitrostyrenes 180a-l under mild reaction conditions was reported, which gave excellent chemical yields (up to 99%) and enantioselectivities (up to 98% ee) via using tert-butanylsulfinylphosphine as a ligand (Table 65). This approach provides a promising route for the synthesis of chiral 2,2-bisarylethylamines 208a-y with excellent chemical yields and ee (Scheme 103).…”