Enantioselective Phosphine Organocatalysis

Abstract

The broad potential synthetic usefulness of phosphinepromoted reactions has stimulated many recent investigations on enantioselective variants of known reactions of this family, as well as the search for new, specifically designed, chiral phosphorus catalysts. This short overview summarizes the state of the art in this field and highlights the most significant achievements, with special emphasis on our recent work.

Cobalt-Catalyzed, Aminoquinoline-Directed Functionalization of Phosphinic Amide sp2 C–H Bonds

“…A related 2-pyridylsulfonyl group is efficient in directing the functionalization of amino acid sp 3 C–H bonds. 10 Since phosphorus-containing compounds are important as pesticides, as organocatalysts, and in materials chemistry, 11 we decided to investigate C–H bond functionalization of phosphinamides possessing an aminoquinoline directing group. Relatively few examples of phosphorus-containing directing groups in catalytic sp 2 C–H bond functionalization have been disclosed, and nearly all of these employ second-row transition metals.…”

Palladium-catalyzed, aminoquinoline-directed arylation of phosphonamidate and phosphinic amide sp3 C–H bonds

“…4 Consequently, we decided to investigate C–H bond functionalization of phosphinamides possessing an aminoquinoline directing group. We have reported a method for cobalt-catalyzed, aminoquinoline-directed coupling of phosphinic amide sp 2 C–H bonds with alkynes, alkenes, and allyl pivalate (Scheme 1).…”

Syntheses of Spirocyclic Oxindole‐Butenolides by Using Three‐Component Cycloadditions of Isocyanides, Allenoates, and Isatins

“…[8,9] Following the pioneering efforts of Lu and Zhang, [10] further applications of this annulation strategy to the total syntheses of natural products and the development of their asymmetric variants have also been well-established. [11,12] Generally, in situ formation of a zwitterionic intermediate, stemmed from the nucleophilic addition between allenoate and phosphine, was believed to be crucial to the success of the above cycloaddition approach.…”