C-Phosphanylated sulfoximines: synthesis and applications in asymmetric allylic substitution reactions

Synthesis of Phosphanyl Sulfoximines Through Phospha‐Michael Reaction of Alkenyl Sulfoximines and Their Evaluation as Chiral Bidentate 1,5‐N,P Ligands for Palladium in Asymmetric Allylic Alkylation

“…[3] Amongst the various sulfoximines which have been designed for transition metals [4] the aryl phosphanyl sulfoximine I [5] and alkyl phosphanyl sulfoximine II [6] ( Figure 1) [7,8] showed considerable promise as 1,4-N,P ligands in Ir-catalyzed asymmetric hydrogenation [4n,4o,5] and Pd-catalyzed allylic alkylation. [5,6] We envisioned the synthesis and study of acyclic and cyclic phosphanyl sulfoximines of type V and VI, respectively, as potential ligands for transition metals.…”

“…[5,6] We envisioned the synthesis and study of acyclic and cyclic phosphanyl sulfoximines of type V and VI, respectively, as potential ligands for transition metals. Phosphanyl sulfoximines V and VI, which have besides the chiral sulfoximine group also a chi-onate anion in the presence of a cyclic N-benzyl-substituted phosphanyl sulfoximine gives the corresponding malonate with 97 % ee in 98 % yield.…”

“…While mainly intramolecular MRs of alkenyl sulfoximines with O-, [14] N-, [15] S- [16] and C-nucleophiles [17] are well documented, only one example of a intermolecular PMR of a vinyl sulfoximine had been described. [6] Therefore, the evaluation of the potential of the PMR for the synthesis of phosphanyl sulfoximines was of interest. In this paper we describe the synthesis of phosphanyl sulfoximines of type V and VI through PMR of alkenyl sulfoximines and their evaluation as ligands in Pd 0 -catalyzed allylic alkylation [18] together with a NMR spectroscopic determination of the mode of their coordination to the Pd atom.…”

SNAAP Sulfonimidate Alkylating Agent for Acids, Alcohols, and Phenols

“…18,19,20,25,26 Most of these methods required sulfinyl chloride 25 and sulfonimidoyl chloride precursors, which were combined with alkoxides or alcohols and triethylamine in situ. 18,19,27,28 Reggelin and co-workers have reported 29 extensively on chiral cyclic sulfonimidates prepared from sulfonimidoyl chlorides.…”

Synthesis of Bis(4-methylphenylsulfonimidoyl)methane - The First ‘Free' Geminal Bis(sulfoximine)

“…15 Naturally, due to the achirality of the ligand, all products were formed as racemic mixtures. To render the process enantioselective we were interested in chiral analogues of the bis(iminophosphorane)s. Some years ago we 16,17 and others [18][19][20][21][22] demonstrated the applicability of sulfoximines in general and bis(sulfoximine)s 17 in particular as chiral ligands in metal-catalyzed reactions. Based on our work with the latter compounds we anticipated that bis(sulfoximine)-based ligands such as 2 may act as a chiral equivalent of the bis(iminophosphorane) 1.…”