Atom‐Efficient Vinylic Arylations with Triarylbismuths as Substoichiometric Multicoupling Reagents under Palladium Catalysis

Abstract

The first atom-efficient arylation of vinylic iodides was achieved by using triarylbismuths as substoichiometric multicoupling reagents under palladium catalysis. Vinylic iodides were efficiently coupled with electronically divergent

Copper‐Catalyzed β‐Iodovinylation of Carbamates: Expedient Access to Highly Functionalized Vinyl‐Carbamates

“…When submitted to a Suzuki‐Miyaura cross‐coupling reaction with phenyl boronic acid under Jana's conditions, 3 f afforded the arylated product 11 in fair yield. Arylation of 3 f through palladium cross‐coupling with triphenylbismuthine using modified Rao's conditions afforded the same product with a similar yield. Stille cross‐coupling reaction between 3 f and tributyl(vinyl)tin using Mee's protocol provided diene 12 in acceptable yield while Heck reaction between 3 f and t ‐butyl acrylate using Okitsu's conditions led to diene 13 in good yield.…”

Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond

“…Miyaura and co-workers reported asymmetric palladium(II) catalysed 1,4-addition reactions of triphenylbismuth to cyclic and acyclic enones, also in aqueous media, with enantiomeric excesses of up to 95% [19]. Further studies include the use of triphenylbismuth in the cross-coupling of aryl bromides and iodides [17,18,20,21,23], acyl chlorides [22,28], vinyl iodides [24], allyl acetates [26] and ␣-arylacetyl chlorides [25]. Wang and co-workers recently demonstrated the compatibility of bismuth reagents with the use of a heterogeneous catalytic system [32].…”

“…Significant recent study has focussed on applications in catalysis, where bismuth species can act as cross-coupling agents in carbon-carbon [15][16][17][18][19][20][21][22][23][24][25][26], carbon-nitrogen [27] and carbon-oxygen [28] bond forming reactions. The low toxicity and ease of handling of arylbismuth compounds makes them comparable with organoboronic acids used in Suzuki-Miyaura type reactions, how- ever, the ability of triarylbismuth compounds to deliver three aryl groups per molecule allows atom-efficient reactions to be developed [29].…”

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

“…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]. In particular, the palladium-catalyzed cross-couplings of allyl bromide [37,38] with triarylbismuths were reported earlier.…”