The Phosphinamide-Based Catalysts: Discovery, Methodology Development, and Applications in Natural Product Synthesis

Abstract

work describes the development of the method for synthesizing P-stereogenic phosphinamides via desymmetric enantioselective C−H arylation.• Qin, X.-L.; Li, A.; Han, F.-S. Desymmetric enantioselective reduction of cyclic 1,3-diketones catalyzed by a recyclable P-chiral phosphinamide organocatalyst. J. Am. Chem. Soc. 2021, 143, 2994 This work describes the application of the P-stereogenic phosphinamides as organocatalysts in desymmetric enantioselective reduction of cyclic 1,3-diketones and the mechanistic study.

Synthetic Studies on the Synthesis of Toxicodenane A and 8,11-epi-Toxicodenane A

“…Admittedly, the desymmetric enantioselective reduction of cyclic 1,3-diketones has been widely investigated, including CBS, enzyme, and transition-metal-catalyzed reductions . We demonstrated that the P -stereogenic phosphinamide catalysts exhibit several important advantages over the reported methods in terms of the overall catalytic efficiency, such as the broad substrate compatibility, high stereo- and diastereoselectivity, the convenience of scale up and operation, and most significantly the ease of structural diversification as well as good the stability and recyclability of catalysts. , …”

A formal synthesis of (–)-erinacine B enabled by asymmetric organocatalysis

“…Erinacines are a branch of the cyathane diterpenoids incorporated with the featured 5-6-7 tricyclic carbocycle decorated with xylose on the cycloheptane moiety. 1 As selectively depicted in Fig. 1, with the exception of erinacine A ( 1 ), erinacines contain a trans -fused 6-7 ring system and 1,4- anti angular-methyl quaternary carbon centers.…”

“…A multitude of innovative synthetic strategies for forging the 5-6-7 skeleton have been developed. 1,3 As selectively depicted in Fig. 2, Snider and co-workers 3 a reported the first total synthesis of (+)-erinacine A by taking advantage of palladium-catalyzed carbonylation of dienyl triflate and carbonyl ene reaction, constructing the 5-6-7 framework in seven steps (Fig.…”

Synthesis of Phosphinic Amides from Chlorophosphines and Hydroxyl Amines via P(III) to P(V) Rearrangement

“…14 In addition, phosphinic amides serve as effective directing groups 15 or ligands 16 for transition-metal catalysis or are used as organocatalysts themselves. 17 Traditional methods for the synthesis of phosphinic amides 11 include the treatment of phosphinic halides with amines, 18 a two-step reaction of phosphine chloride with amines followed by oxidation, 19 and the condensation of phosphinic acids with amines under certain conditions. 20 A range of new methods for the construction of phosphinic amides have appeared in recent years.…”

“…Phosphinic amides, with the structure R 2 P­(O)­NR 2 , are a type of important organophosphorus compound showing multifaceted properties, such as biological activity, light-emitting behavior, and flame-retardant property . In addition, phosphinic amides serve as effective directing groups or ligands for transition-metal catalysis or are used as organocatalysts themselves . Traditional methods for the synthesis of phosphinic amides include the treatment of phosphinic halides with amines, a two-step reaction of phosphine chloride with amines followed by oxidation, and the condensation of phosphinic acids with amines under certain conditions …”