Palladium-catalysed α-allylation of chiral sulfinimines derived from symmetric cyclic ketones

Transition metal-catalyzed reactions of N-sulfinyl imines

“…In the case of imines derived from cyclic ketones 51, their allylation with allyl carbonate 52 in the presence of Pd 2 dba 3 and P (nBu) 3 allowed the formation of the corresponding a-monoallylated compounds 53 with high yields and diastereoselectivities (Scheme 19) [30]. The same reactions with methallyl or 3-phenylallyl carbonate afforded the corresponding products with similar results.…”

Asymmetric Synthesis of Pyrrolidine‐Containing Chemical Scaffolds via Tsuji–Trost Allylation of N‐tert‐Butanesulfinyl Imines

“…Prior to applying the optimised reaction conditions of the allylation, the focus was turned on the synthesis of required starting N ‐tert ‐butanesulfinyl imines 1 a – l . This was achieved by following Ellman's protocol, in yields ranging from 57 to 92 % (see the Supporting Information) .…”

“…In particular, under mild reaction conditions, compounds bearing an allyl group at the α‐position of chiral N ‐tert ‐butanesulfinyl imines were obtained in high yields, with good diastereoselectivity and substrate tolerance. In a following report, the α‐allylation of chiral N ‐tert ‐butanesulfinyl imines derived from symmetric cyclic ketones was reported . Hence, we envisioned taking advantage of the Tsuji–Trost allylation of N ‐tert ‐butanesulfinyl imines to access, in five steps, pyrrolidine‐based chemical scaffolds as outlined in Scheme .…”

Transition Metal-Catalyzed α-Position Carbon–Carbon Bond Formations of Carbonyl Derivatives

“…The chiral ketone 74 is obtained via simple hydrolysis of the chiral α-allylated imine 73 without racemization. The same group extended their strategy to include various allyl carbonate precursors, and the linear mono-allylated products were obtainable from a range of cyclic chiral sulfinimines [43]. The construction of chiral quaternary carbons at the α-position of chiral sulfinimines was proposed by Yang and coworkers in 2018 (Scheme 30) [44].…”

“…Pd catalyst and monodentate phosphine ligand Aldehydes Allylation [14] Arylation [15][16][17] Imines Allylation [41][42][43] Pd catalyst and DPPF ligand Ketones Allylation [33,34] Pd catalyst and diphenylbisphosphine ligand Ketones Allylation [31] Amides Allylation [46,47] Pd catalyst and dialkylbisphosphine ligand Amides Arylation [48] Pd catalyst and pyrrolidine organocatalyst Aldehydes Allylation [18,19] Pd catalyst and phosphoric acid Aldehydes Allylation [20][21][22][23] Pd catalyst and DIAPHOX ligand Ketones Allylation [32] Ru catalyst and PNN ligand Amides Alkylation [49] Rh catalyst and BINAP ligand Aldehyde Allylation [25] Ir catalyst and P-olefin & amine Aldehydes Allylation [24] Ir catalyst and monodentate phosphine ligand Esters Alkylation [50] Ni catalyst and Mandyphos ligand Amides Acylation [51] Co catalyst and PNP ligand Ketones Alkylation [37] Co catalyst and PN 5 P ligand Amides Esters Alkylation [52] Mn catalyst and PN n P ligand Ketones Alkylation [36,38] Ni catalyst and NNN ligand Amides Esters Alkylation [53] Rh catalyst and NHC ligand Ketones Alkylation [39] Ru(bpy) 3 photocatalyst Aldehydes Alkylation [26,27,30] Ketones Alkylation [40] Imines Alkylation [45] Ir photocatalyst Aldehydes Alkylation [28,29] Catalysts Allylic alkylation and ...…”