Oxalates as Activating Groups for Alcohols in Visible Light Photoredox Catalysis: Formation of Quaternary Centers by Redox-Neutral Fragment Coupling.

Alkyl oxalates are new bench-stable alcohol-activating groups for radical generation under visible light photoredox conditions. Using these precursors, the first net redox-neutral coupling of tertiary and secondary alcohols with electron-deficient alkenes is achieved

Organocatalytic Vinyl and Friedel−Crafts Alkylations with Trifluoroborate Salts

Herein we report the first use of vinyl and heteroaryl trifluoroborate salts as viable substrates for amine-catalyzed conjugate additions. The application of LUMO-lowering iminium catalysis has enabled the highly regio- and enantioselective 1,4-addition of rationally designed trifluoroborate salt nucleophiles to α,β-unsaturated aldehydes. Imidazolidinone 2•HCl was found to catalyze the addition of various BF_3K-derived heteroaryl and vinyl species to a range of enals with excellent levels of enantioselectivity. Importantly, the use of these salts can enable nontraditional regiocontrol as part of a Friedel−Crafts pathway. Boronic acids can also be employed as viable π-nucleophiles for these asymmetric conjugate additions provided that in situ activation to the corresponding boronate species is accomplished. While BF_3K salts are routinely employed in transition metal catalysis, to our knowledge, this is the first use of this activation group for organic catalysis or Friedel−Crafts alkylations

Development of a New Lewis Acid-Catalyzed [3,3]-Sigmatropic Rearrangement: The Allenoate-Claisen Rearrangement

A new Lewis acid-catalyzed Claisen rearrangement has been developed that allows the stereoselective construction of β-amino-α,β,ε,ζ-unsaturated-γ,δ-disubstituted esters from simple allylic amines and allenoate esters. This reaction, which is contingent upon the use of Lewis acid, can be conducted with a range of metal salts (Yb(OTf)_3, AlCl_3, Sn(OTf)_2, Cu(OTf)_2, MgBr_2·Et_2O, FeCl_3, Zn(OTf)2) with catalyst loadings as low as 5 mol %. This catalytic process provides access to a diverse range of β-amino-α,β,ε,ζ-unsaturated-γ,δ-disubstituted esters in high yield and with excellent levels of diastereoselectivity for a series of allyl pyrrolidines (R_1 = H, Me, i-Pr, Ph, NR_2 = pyrrolidine, piperidine, Nme_2; ≥81% yield, ≥94:6 syn:anti) and allenoate esters (R_2 = H, Me, i-Pr, Ph, allyl, NPht, Cl; ≥75% yield, ≥91:9 syn:anti). The capacity of this new Claisen rearrangement to provide catalytic access to elusive structural motifs has also been demonstrated in the stereospecific formation of quaternary carbon bearing frameworks arising from geranyl- and neryl pyrrolidine (≥93% yield, >98:2 dr)

Enantioselective Organocatalytic Cyclopropanations. The Identification of a New Class of Iminium Catalyst Based upon Directed Electrostatic Activation

A new method for enantioselective organocatalytic cyclopropanation is described. This study outlines the identification of a new class of iminium catalyst based on the concept of directed electrostatic activation (DEA). This novel organocatalytic mechanism exploits dual activation of ylide and enal substrates through a proposed electrostatic activation and stereodirected protocol. Formation of trisubstituted cyclopropanes with high levels of enantio- and diastereoinduction is accomplished for a variety of α,β-unsaturated aldehydes and sulfonium ylides. In addition, mechanistic studies have found that this cyclopropanation reaction exhibits enantioselectivity and reactivity profiles that are in accord with the proposed DEA step