Snapshots of a Stille reaction

Casado, Arturo L.; Espinet, Pablo; Gallego, Ana M.; Martínez‐Ilarduya, Jesús M.

doi:10.1039/b008811k

Cited by 66 publications

(64 citation statements)

References 11 publications

(6 reference statements)

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“…In some instances it is the oxidative addition [96] or the reductive elimination [97] that controls the rate of the reaction. The actual Pd species in solution can be different from those introduced initially as a catalyst or formed directly in the oxidative addition, as discussed below.…”

Section: The Lower Cycle Includes and Expands On Open Mechanisms It mentioning

confidence: 99%

“…[96] Similarly, the oxidative addition of C 6 F 5 OTf to complexes [Pd(dppe)(olefin)] extremely slow, but can be accelerated very efficiently by adding LiCl, which promotes the ready formation of [PdRCl(dppe)] (Scheme 16). [97] A recent study showed that the oxidative addition of alkenyl triflates to [Pd(PPh 3 ) 4 ] in DMF gives [Pd(h 1 -alkenyl)(PPh 3 ) 2 (dmf)](TfO) under stoichiometric conditions (Tf = trifluoromethanesulfonyl). [98] The following reactivity order was established: alkenyl-OTf @ vinyl-Br > PhBr and vinyl-OTf @ PhOTf.…”

Section: Oxidative Addition With [Pd 2 (Dba) 3 ]mentioning

confidence: 99%

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The Mechanisms of the Stille Reaction

2004

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Eighteen years ago in Angewandte Chemie John K. Stille reviewed a novel methodology, which eventually became known by his name, for the coupling of organostannanes with organic electrophiles. Since then that seed has blossomed into a multifaceted methodology full of hidden possibilities to explore, discover, and enjoy. Very recent modifications are making synthetic wishes come true that were only dreamed of a few years ago. Moreover, as important advances are being made in the understanding of the mechanistic details of the process, it is becoming increasingly possible to apply this essential reaction and its new variants in a less empirical way. The purpose of this Review is to give a critical account of this progress.

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Section: The Lower Cycle Includes and Expands On Open Mechanisms It mentioning

confidence: 99%

Section: Oxidative Addition With [Pd 2 (Dba) 3 ]mentioning

confidence: 99%

The Mechanisms of the Stille Reaction

2004

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“…It might also operate in the presence of an excess of L and with easily leaving anionic ligands lacking bridging ability, in which case transmetallation proceeds from cationic complexes 67. This mechanism is also followed in the coupling aryl triflates with vinyl tributyl stannane in the presence of dppe as the ligand [151]. The fact that the transmetallation step in the Stille reaction can follow two different paths -S E 2(cyclic) and S E 2(open) -has important stereochemical consequences, as this transformation determines the stereochemical outcome of the overall coupling reaction for C(sp 2 )-X electrophiles.…”

Section: Dissociative Mechanistic Proposalsmentioning

confidence: 99%

“…16 A study of the coupling of aryl triflates with organostannanes by Espinet led to the conclusion that an open transition state operates in cases where no bridging groups are available on the coordination sphere of Pd(II) to produce a cyclic intermediate [150,151]. The S E 2(open) transmetallation mechanism, proceeding through transition state 64, is summarized in Scheme 1-29.…”

Section: Dissociative Mechanistic Proposalsmentioning

confidence: 99%

Mechanistic Aspects of Metal‐Catalyzed C—C and C—X Bond‐Forming Reactions

Echavarren

Cárdenas

2005

ChemInform

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Cross-coupling reactions, such as the Stille reaction of organostannanes [1][2][3] and the Suzuki (or Suzuki-Miyaura) cross-coupling of organoboron compounds [4] have settled amongst the more general and selective palladium-catalyzed cross-coupling reactions [5] (Scheme 1-1). These reactions are closely related to other cross-couplings based on transmetallations of a variety of hard or soft organometallic nucleophiles [6] such as the Hiyama [7,8], Sonogashira [9], Kumada (or Kumada-Corriu), and other related couplings [10][11][12].Coupling reactions are somewhat related to the Heck alkenylation of organic electrophiles [13, 14], which is often referred to in the literature as a coupling process. However, although the first steps in both processes are identical, in the Heck reaction there is no transmetallation step. In the alkenylation reaction, the C-C bond is formed by an insertion process, which is followed by a b-hydride elimination to form the substituted alkene product. Cross-coupling (transmetallationbased) processes are a family of closely related catalytic processes that share most mechanistic aspects, although some differences exist on the activation of the organometallic nucleophile. So far, most of the detailed mechanistic studies have cen-

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“…180 Transmetalation equilibria between organogold and organopalladium complexes. shown in Scheme 57 has been studied.…”

Section: Scheme 54mentioning

confidence: 99%