Chiral Hypervalent Iodine(III) Catalyst Promotes Highly Enantioselective Sulfonyl- and Phosphoryl-oxylactonizations

Abstract

An efficient enantioselective hypervalent iodine promoted oxylactonization of 4-pentenoic acids has been achieved using stoichiometric or a catalytic amount of chiral aryl-λ-iodane. This reaction provides straightforward access to a wide range of sulfonyloxy- and phosphoryloxy-γ-butyrolactones in respectable yields with moderate to excellent enantioselectivities.

Recent Application of Chiral Aryliodine Based on the 2-Iodo­resorcinol Core in Asymmetric Catalysis

“…In order to inhibit the background reaction in the oxidative system, both reactions require low temperatures to reduce oxidation of the C=C bond by mCPBA. 28 In 2016, the Jacobsen group synthesized a chiral aryliodine based on the 2-iodoresorcinol core, introducing an ester group at C-4 of the benzene ring. Trisubstituted cinnamamide derivative 39 underwent enantioselective vicinal difluorination using the best catalyst 5h, mCPBA as the oxidant, and pyridine•9HF as the nucleophilic fluorine source to give product 40 with excellent enantioselectivity and diastereoselectivity (up to 93% ee, >19:1 dr) (Scheme…”

Alkene Difunctionalization Using Hypervalent Iodine Reagents: Progress and Developments in the Past Ten Years

“…A combination of a catalytic amount of PhI and mCPBA promoted alkenoic acid 110 cyclization with phosphate to yield lactone 112 . Recently, Masson et al developed the first enantioselective sufonyloxy- and phosphoryloxy-oxylactonization reaction using a catalytic lactamide-based chiral iodine and mCPBA combination (Scheme 21b) [79]. A diverse range of substrates 113 were subjected to either sulfonic acid or phosphoric acid nucleophile, resulting in cyclized adducts 114 and 115 with moderate to good enantioselectivity.…”

Recent advances in hypervalent iodine(III)-catalyzed functionalization of alkenes

“…The enantioselective control mode is the same as that described in stoichiometric reactions [ 49 ]. Recently, Masson and co-workers described an enantioselective iodoarene-catalyzed sulfonyl- and phoshoryloxylactonization of alkenoic acids 11 with additional nucleophiles ( Scheme 4 , bottom) [ 50 ], in which a bisamide chiral precatalyst was applied [ 51 ]. This reaction provides an efficient access to various interesting enantioenriched γ-lactones through a tandem sequence in acceptable yields and moderate to excellent enantioselectivities.…”