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

Abstract

Rh-catalyzed asymmetric 1,4-addition reactions to a,b-unsaturated carbonyl and related compounds: an update Available online xxxx Dedicated to my son, OMID on the occasion of his 35th birthday. a b s t r a c tThe Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to an appropriate receptor has been a growing area of research over the last decade. The receptors for such a 1,4-addition reaction are chiefly a,b-unsaturated ketones, esters, amides, enones, nitroalkenes, and occasionally phosphonates etc. This reaction in the presence of chiral rhodium complexes introduce the aryl and alkenyl groups at the b-position of the above electron poor olefins, enantioselectively. Chiral Rh complexes similar to other transition metals can be added to some electron poor olefins, in turn making them viable to attack by various organometallic reagents for highly enantioselective C-C bond formation. The Rh-catalyzed asymmetric 1,4-addition of organometallic reagents to electron poor olefins has been reviewed in 2003. Due to the importance of the asymmetric C-C bond formation via 1,4-conjugate addition reactions and the number of such reactions catalyzed by Rh-complexes, in this review we highlight the recent advances in Rh-complex asymmetric catalyzed 1,4-addition reactions since 2003.

Applications of Dainshefsky's Dienes in the Asymmetric synthesis of Aza‐Diels‐Alder Reaction

“…We are interested in heterocyclic chemistry and their asymmetric synthesis . We have recently reviewed the applications of DA and HDA reactions in the total synthesis of natural products ,.…”

Chiral N-aryl tert-butanesulfinamide-olefin ligands for rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to cyclic enones

“…28 As we know, sulfinamide-olefin compounds are recently used as chiral ligand in highly enantioselective rhodium-catalyzed asymmetric 1,4-addition reaction of arylboronic acids to ,-unsaturated carbonyl compounds, [29][30] which has extensive applications in medicinal synthesis and natural synthesis, 31 and has achieved great progress. [32][33][34][35][36][37][38][39] Furthermore, the C-N coupling reaction products are seldom directly used as chiral ligands. [40][41] Therefore we would like to explore the application of the C-N coupling products chiral N-aryl tert-butanesulfinamide-olefin ligands in rhodium-catalyzed asymmetric 1,4-addition reaction of arylboronic acids to cyclic enones (Scheme 1).…”

Asymmetric Alkenylation of Enones and Imines Enabled by A Highly Efficient Aryl to Vinyl 1,4‐Rhodium Migration

“…[1] Compared to the wide application of arylboronates,v inylboronates are far less studied, and quite limited with the easily accessible ones bearing adi-substituted double bond. [1] Compared to the wide application of arylboronates,v inylboronates are far less studied, and quite limited with the easily accessible ones bearing adi-substituted double bond.…”

“…Enantioselective rhodium-catalyzed addition of organoboron reagents to electron-deficient double bonds has proven to be apowerful and reliable method for asymmetric carbon-carbon bond construction. [1] Compared to the wide application of arylboronates,v inylboronates are far less studied, and quite limited with the easily accessible ones bearing adi-substituted double bond. [2] When vinylboronates with more substitutions on the double bond are needed, one of the challenges aroused is to control the olefin stereochemistry.A lthough several methods to effectively prepare these vinylboronates have been described, [3] new and even more ingenious strategies to address this issue are always desirable.…”