Palladium-catalyzed cross-coupling reaction of allyl carbonates with organostannanes

Palladium-catalyzed cross-couplings of allylic carbonates with triarylbismuths as multi-coupling atom-efficient organometallic nucleophiles

“…The reactivity profile of allylic carbonates differ from other allylic substrates in coupling reactions [11][12][13][14][15][16][17][18][19][20][21][22]. The coupling reaction of allylic carbonate in the presence of palladium catalyst usually involves p-allylpalladium(II) intermediate species [17] through the initial oxidative addition of allylic carbonate to Pd(0) with subsequent loss of carbon dioxide.…”

“…The cross-coupling reactions of various allylic substrates with organo-boron, -tin, -silicon, -indium, etc. reagents were reported under palladium-catalyzed conditions [11][12][13][14][15][16][17][18][19][20][21][22]. However, recently triarylbismuths have been demonstrated to be useful as multi-coupling organometallic nucleophiles for atom-efficient couplings with organic electrophiles [23][24][25][26][27][28][29][30][31][32][33][34][35][36].…”

Stereoselective synthesis of the C14 C23 fragment of biselyngbyolide A and B enabled by transition metal catalysis

“…This was accomplished using the “ligand-free” Pd-catalyzed coupling conditions first reported by Echavarren. 15,16 These conditions were attractive due to their mild nature and their ability to deliver skipped dienes with high yield and regioselectivity. In this case, the C19–C20 bond was formed with complete Z / E selectivity for the trisubstituted alkene and excellent (>10:1) branched/linear selectivity.…”

Balancing fertility management and economics in organic field vegetable rotations

“…Our exploratory Stille cross‐coupling studies are shown in Scheme . We were mindful that the intermediate π‐allylpalladium complex 16 could arise from the two regioisomeric carbonates 17 and 18 , and furthermore that the configuration of both the internal C40 carbonate of 17 (at the allylic stereocenter) and terminal C42 carbonate of 18 (olefin isomers) may well be important, as the rate of isomerization of π‐allyl species derived from such precursors depend strongly on the choice of reaction conditions 11a. In the present system, the combination of a hindered Z stannane combined with the bulky nature of the tricyclic DEF system was anticipated to favor terminal substitution and formation of an E olefin.…”