Enantioselective Synthesis of Dialkylated N-Heterocycles by Palladium-Catalyzed Allylic Alkylation

Abstract

Determination of absolute stereochemistry by a combinedVibrational Circular Dichroism (VCD) spectroscopic and computational chemistry approach SI 44

Palladium-Catalyzed Asymmetric Allylic Alkylation Strategies for the Synthesis of Acyclic Tetrasubstituted Stereocenters

“…55 An -hydroxy ester 191 was accessed by hydrolysis of the DAAA product 190 in the presence of catalytic methanol and sulfuric acid. 56 The method additionally was also performed using a sulfur-containing lactam, an allyl 2-methyl-3-oxothiomorpholine-2-carboxylate, although derivatization of the product to the acyclic precursor was not demonstrated.…”

Palladium-Catalyzed Decarboxylative Carbonylative Transformation of Benzyl Aryl Carbonates: Direct Synthesis of Aryl 2-Arylacetates

“…Compared with traditional cross-coupling reactions; decarboxylative coupling reactions are milder and more environmentally friendly. Carboxylic acids or carbonatese, as the applied substrates, are nontoxic, stable, and readily available. , As expected, palladium-catalyzed decarboxylative carbonylations have also been reported . In 2011, Lee and co-workers reported a palladium-catalyzed decarboxylative carbonylation of aryl alkynyl carboxylic acids and aryl iodides for synthesis of α,β-alkynyl ketone under CO pressure (10 bar) .…”

“…Based on the experimental data and precedents regarding relevant palladium-catalyzed carbonylation reactions, , a possible reaction pathway is proposed and shown in Scheme . Initially, the reactive Pd 0 species was generated by the ligand exchange, followed by the oxidative addition with 1a to form IM1 .…”

Palladium‐Catalyzed Decarboxylative Asymmetric Allylic Alkylation: Development, Mechanistic Understanding and Recent Advances

“…Furthermore, Stoltz extended the scope of this reaction to a number of N,O‐ and N,S‐heterocycles 92 (Scheme ) . Excellent ee s were obtained for morpholinone and oxazolidin‐4‐one substrates (up to 99% ee ) while the thiomorpholinone substrate gave a slight decrease in ee ( 93 Y=CH 2 , X=S, R=Me; 86% ee ).…”