S_N1‐Type Reactions in the Presence of Water: Indium(III)‐Promoted Highly Enantioselective Organocatalytic Propargylation of Aldehydes

Enantioselective cooperative catalysis

“…alkynes and active methylenes were simultaneously activated by the catalysts. 64 The mechanism of the reaction is similar to that described in Scheme 65 and typically involves formation of propargylic cations which were attacked by the enamines (cf. 242) resulting in the formation of propargylic alkylated products 240 through several bond-breaking and bond-forming processes.…”

Desilylation‐Activated Propargylic Transformation: Enantioselective Copper‐Catalyzed [3+2] Cycloaddition of Propargylic Esters with β‐Naphthol or Phenol Derivatives

“…[1][2][3][4] Very recently,wedisclosed the first copper-catalyzed asymmetric formal [3+ +2] cycloaddition of propargylic esters as C 2 synthons with C,O-bis(nucleophile)s, b-ketoesters,b yasequential propargylic alkylation/intramolecular hydroalkoxylation process. [5] However,t he use of other bis(nucleophile)s for this cycloaddition remains unexplored.…”

Cooperative Catalysis: Enantioselective Propargylic Alkylation of Propargylic Alcohols with Enecarbamates Using Ruthenium/Phosphoramide Hybrid Catalysts

“…However, unfortunately, available nucleophiles are quite limited in these cooperative catalytic reaction systems. [7] Based on this background, we have now designed novel hybrid catalysts such as thiolate-bridged diruthenium complexes bearing a phosphoramide moiety which is based on the BINOL skeleton (1).[8] The phosphoramide moiety in the ruthenium complex may activate nucleophiles such as enecarbamates [9] and control the nucleophilic attack by the allenylidene ligand on the ruthenium complexes (Scheme 2).In this reaction system, the intramolecular organocatalyst plays a crucial role in achieving high enantioselectivity. Herein, we report the reactions undergoing cooperative catalysis using hybrid transition-metal complexes bearing an organocatalyst.…”