Rhenium(I)‐Catalyzed Generation of α,β‐Unsaturated Carbene Complex Intermediates from Propargyl Ethers for the Preparation of Cycloheptadiene Derivatives

Abstract

The rhenium(I)‐catalyzed generation of α,β‐unsaturated carbene complex intermediates from easily available propargyl ethers was achieved for the concise construction of cycloheptadiene derivatives through the formal [4+3] cycloaddition reaction with siloxydienes.

Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis

“…Iwasawa and Sogo reported the novel fragmentation of propargylic ether 683, mediated by the hydride transfer of rhenium vinylidene 687 (Scheme 139). 337 Rhenium carbene 686, arising from this retro-ene-type process, undergoes [2 + 1] cycloaddition with silyl enol ether 688 to provide cyclopropane 693. This cyclopropane then yields cycloheptadiene 690 after a [3,3]-sigmatropic rearrangement.…”

Dearomative [4 + 3] cycloaddition of furans with vinyl-N-triftosylhydrazones by silver catalysis: stereoselective access to oxa-bridged seven-membered bicycles

“…[1][2][3][4][5][6][7] Over the past few decades, the [4 + 3] cycloaddition between 1,3-dienes and vinylcarbenes has been established as the most promising strategy for the stereoselective synthesis of these complex ring systems, as demonstrated by a variety of complex natural products synthesis. [8][9][10][11][12][13] Major efforts in this arena so far have been dedicated to the use of vinyl diazo compounds, [14][15][16][17][18] propargyl esters, [19][20][21] 4-alkenyl-1,2,3-triazoles, 22,23 enynes, [24][25][26][27] allenes, 28,29 and 7-vinyl-1,3,5-cycloheptatrienes 30 as the sources of vinylcarbene partners to access 1,4cycloheptadienes (Fig. 1a).…”

Dearomative [4 + 3] cycloaddition of furans with vinyl-N-triftosylhydrazones by silver catalysis: stereoselective access to oxa-bridged seven-membered bicycles

“…[1][2][3][4][5][6][7] Over the past few decades, the [4 + 3] cycloaddition between 1,3-dienes and vinylcarbenes has been established as the most promising strategy for the stereoselective synthesis of these complex ring systems, as demonstrated by a variety of complex natural products synthesis. [8][9][10][11][12][13] Major efforts in this arena so far have been dedicated to the use of vinyl diazo compounds, [14][15][16][17][18] propargyl esters, [19][20][21] 4-alkenyl-1,2,3-triazoles, 22,23 enynes, [24][25][26][27] allenes, 28,29 and 7-vinyl-1,3,5-cycloheptatrienes 30 as the sources of vinylcarbene partners to access 1,4cycloheptadienes (Fig. 1a).…”