Alkynes as Stille Reaction Pseudohalides:  Gold- and Palladium-Cocatalyzed Synthesis of Tri- and Tetra-Substituted Olefins

Shi, Yili; Peterson, Sonja; Haberaecker, Walter W.; Blum, Suzanne A.

doi:10.1021/ja710648b

Cited by 127 publications

(79 citation statements)

References 22 publications

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“…In contrast to our previous reports of Pd/Au cocatalyzed reactions, 3,4 however, this reaction displayed a slow but nonzero background reaction with Pd 2 dba 3 alone.…”

Section: Resultscontrasting

confidence: 99%

“…18 We have previously demonstrated that combining the distinct reactivities of Au(I) and Pd(0) catalysts allows for new reactivity unavailable to single-metal systems. 3,4,19 Herein, we describe a new Au(I) and Pd(0) dual-catalytic system for the rearrangement of alkene-tethered vinyl aziridines and provide insight into the mechanism of this dual-catalytic system.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic Studies of Azaphilic versus Carbophilic Activation by Gold(I) in the Gold/Palladium Dual-Catalyzed Rearrangement of Alkenyl Vinyl Aziridines

et al. 2012

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A vinyl aziridine activation strategy cocatalyzed by palladium(0) and a gold(I) Lewis acid has been developed. This rearrangement installs a C–C and a C–N bond in one synthetic step to form pyrrolizidine and indolizidine products. Two proposed mechanistic roles for the gold cocatalyst were considered: (1) carbophilic gold catalysis or (2) azaphilic gold catalysis. Mechanistic studies support an azaphilic Lewis acid activation of the aziridine over a carbophilic Lewis acid activation of the alkene.

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“…In contrast to our previous reports of Pd/Au cocatalyzed reactions, 3,4 however, this reaction displayed a slow but nonzero background reaction with Pd 2 dba 3 alone.…”

Section: Resultscontrasting

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Mechanistic Studies of Azaphilic versus Carbophilic Activation by Gold(I) in the Gold/Palladium Dual-Catalyzed Rearrangement of Alkenyl Vinyl Aziridines

et al. 2012

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“…[98] The reactions were postulated to proceed through Au I activation of the alkynes toward nucleophilic metalation/oxidative addition to Pd 0 . In view of the results just commented, the authors suggested that their own previous mechanistic proposal in reference [98] should be reinterpreted, to include the intermediacy of a vinyl-gold compound.…”

Section: Carboauration Reactions Of Alkynesmentioning

confidence: 99%

Bimetallic Catalysis using Transition and Group 11 Metals: An Emerging Tool for CC Coupling and Other Reactions

Pérez‐Temprano

Casares

Espinet

2012

Chemistry A European J

211

131

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Bimetallic catalysis refers to homogeneous processes in which either two transition metals (TM), or one TM and one Group 11 (G11) element (occasionally Hg also), cooperate in a synthetic process (often a C-C coupling) and their actions are connected by a transmetalation step. This is an emerging research area that differs from the isolated or tandem applications of the now classic processes (Stille, Negishi, Suzuki, Hiyama, Heck). Most of the reactions used so far combine Pd with a second metal, often Cu or Au, but syntheses involving very different TM couples (e.g., Cr/Ni in the catalyzed vinylation of aldehydes) have also been developed. Further development of the topic will soon demand a good knowledge of the mechanisms involved in bimetallic catalysis, but this knowledge is very limited for catalytic processes. However, there is much information available, dispersed in the literature, coming from basic research on exchange reactions occurring out of any catalytic cycle, in polynuclear complexes. These are essentially the same processes expected to operate in the heart of the catalytic process. This Review gathers together these two usually isolated topics in order to stimulate synergy between the bimetallic research coming from more basic organometallic studies and the more synthetic organic approaches to this chemistry.

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“…The efficient synthesis of polysubstituted alkenes in a regio-and stereoselective fashion is an important goal in organic chemistry [25][26][27][28]. Carbometallation of alkynes is a time-tested technique for the synthesis of substituted alkenes since the resulting alkenylmetals can be transformed to various substituted alkenes in a stereoselectivity [29][30][31][32][33][34]. Polysubstituted vinyl halides are potential precursors of various substituted alkenes due to the versatile reactivity of halogen.…”

Section: Introductionmentioning

confidence: 99%

Regio- and stereospecific synthesis of vinyl halides via carbozincation of acetylenic sulfones followed by halogenation

Xie¹,

Wang²,

Zhang³

et al. 2009

Journal of Organometallic Chemistry

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Alkynes as Stille Reaction Pseudohalides: Gold- and Palladium-Cocatalyzed Synthesis of Tri- and Tetra-Substituted Olefins

Cited by 127 publications

References 22 publications

Mechanistic Studies of Azaphilic versus Carbophilic Activation by Gold(I) in the Gold/Palladium Dual-Catalyzed Rearrangement of Alkenyl Vinyl Aziridines

Mechanistic Studies of Azaphilic versus Carbophilic Activation by Gold(I) in the Gold/Palladium Dual-Catalyzed Rearrangement of Alkenyl Vinyl Aziridines

Bimetallic Catalysis using Transition and Group 11 Metals: An Emerging Tool for CC Coupling and Other Reactions

Regio- and stereospecific synthesis of vinyl halides via carbozincation of acetylenic sulfones followed by halogenation

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