The Phosphine-Catalyzed Alkyne to 1,3-Diene Isomerization Reaction

Abstract

The alkyne to 1,3-diene isomerization reaction is a process in which a nucleophilic phosphine catalyst promotes the rearrangement of an electron-withdrawing group activated alkyne to the corresponding conjugated diene. The origin, mechanism, development, and application of this organocatalytic and stereoselective reaction in the synthesis of complex organic molecules are reviewed.

Iron‐Catalyzed Alkenylzincation of Internal Alkynes†

“…[ 5 ] Therefore, the synthesis of conjugated dienes has been of great interest. [ 6 ] However, the synthesis of multi‐substituted conjugated olefins is highly challenging due to the difficulty in controlling the Z / E selectivity. [ 7 ]…”

Remote Functionalization by Pd-Catalyzed Isomerization of Alkynyl Alcohols

“…Alkynes can also be isomerized into thermodynamically more stable conjugated 1,3-dienes (Figure C; “yne-to-diene” isomerization, I → III ). Even though examples of base and phosphine catalysis have been reported, most of the methods developed rely on the use of late transition metals . In this context, the isomerization of a CC bond driven by the conjugation of the diene to an electron-withdrawing substituent is the most documented strategy.…”

Experimental and Theoretical Study of Phosphine‐Catalyzed Reaction Modes in the Reaction of α‐Substituted Allenes with Aryl Imines

“…Phosphine-catalyzed reactions have become one of the flourished classes of catalytic transformations, which are used to construct a wide array of carbon-carbon/heteroatom bonds. [1][2][3][4][5][6][7] In this context, phosphine-catalyzed reactions of α-substituted allenes with aryl imines have become extremely multifaceted synthetic methodologies for preparing synthetically useful or biologically important heterocyclic compounds and total synthesis of natural products. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] From a mechanistic point of view, the zwitterionic intermediates generated via 1,4-addition of phosphine catalyst to αsubstituted allenes exhibit excellent dipolar-type cycloaddition reactivity toward imines.…”

“…Phosphine‐catalyzed reactions have become one of the flourished classes of catalytic transformations, which are used to construct a wide array of carbon‐carbon/heteroatom bonds [1–7] . In this context, phosphine‐catalyzed reactions of α‐substituted allenes with aryl imines have become extremely multifaceted synthetic methodologies for preparing synthetically useful or biologically important heterocyclic compounds and total synthesis of natural products [8–25] .…”