Acylation, methylation, and carboxyalkylation of olefins by Group VIII metal derivatives

Heck, Richard F.

doi:10.1021/ja01022a034

Cited by 770 publications

(303 citation statements)

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“…These reactions have played an enormously decisive and important role in shaping chemical synthesis and have revolutionized the way one thinks about synthetic organic chemistry. The Heck reaction (Equation (1)) is used extensively in many syntheses, including agrochemical, fine chemicals, pharmaceutical, etc. The reaction was introduced by Mizoroki [8] and Heck [9] independently more than four decades ago.…”

Section: Introductionmentioning

confidence: 99%

Heck Reaction—State of the Art

Jagtap¹

2017

Catalysts

175

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Abstract:The Heck reaction is one of the most studied coupling reactions and is recognized with the Nobel Prize in Chemistry. Thousands of articles, hundreds of reviews and a number of books have been published on this topic. All reviews are written exhaustively describing the various aspects of Heck reaction and refer to the work done hitherto. Looking at the quantum of the monographs published, and the reviews based on them, we found a necessity to summarize all reviews on Heck reaction about catalysts, ligands, suggested mechanisms, conditions, methodologies and the compounds formed via Heck reaction in one review and generate a resource of information. One can find almost all the catalysts used so far for Heck reaction in this review.

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Section: Introductionmentioning

confidence: 99%

Heck Reaction—State of the Art

Jagtap¹

2017

Catalysts

175

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“…density functional theory calculation | homogeneous catalysis | organometallic | regiochemistry W hereas the palladium-catalyzed Mizoroki-Heck coupling is an established powerful strategy for the formation of carbon-carbon bonds from electron-deficient and electron-rich olefins (1)(2)(3)(4)(5), insertion (co)polymerization (6-8) of acceptor or donor substituted olefins has only been demonstrated since the mid-1990s, and only a few catalyst motifs are known to promote such polymerizations (9,10), which are based on palladium. The regioselectivity of insertion follows the same pattern for both reactions.…”

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confidence: 99%

Breaking the regioselectivity rule for acrylate insertion in the Mizoroki–Heck reaction

Wucher

Caporaso

Roesle

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

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In modern methods for the preparation of small molecules and polymers, the insertion of substrate carbon-carbon double bonds into metal-carbon bonds is a fundamental step of paramount importance. This issue is illustrated by Mizoroki-Heck coupling as the most prominent example in organic synthesis and also by catalytic insertion polymerization. For unsymmetric substrates H 2 C ¼ CHX the regioselectivity of insertion is decisive for the nature of the product formed. Electron-deficient olefins insert selectively in a 2,1-fashion for electronic reasons. A means for controlling this regioselectivity is lacking to date. In a combined experimental and theoretical study, we now report that, by destabilizing the transition state of 2,1-insertion via steric interactions, the regioselectivity of methyl acrylate insertion into palladiummethyl and phenyl bonds can be inverted entirely to yield the opposite "regioirregular" products in stoichiometric reactions. Insights from these experiments will aid the rational design of complexes which enable a catalytic and regioirregular MizorokiHeck reaction of electron-deficient olefins.density functional theory calculation | homogeneous catalysis | organometallic | regiochemistry W hereas the palladium-catalyzed Mizoroki-Heck coupling is an established powerful strategy for the formation of carbon-carbon bonds from electron-deficient and electron-rich olefins (1-5), insertion (co)polymerization (6-8) of acceptor or donor substituted olefins has only been demonstrated since the mid-1990s, and only a few catalyst motifs are known to promote such polymerizations (9, 10), which are based on palladium. The regioselectivity of insertion follows the same pattern for both reactions. Electron-deficient olefins [e.g., methyl acrylate (MA)] selectively insert in a 2,1-fashion (6, 9-11), whereas electron-rich olefins (e.g., vinyl ethers) insert in a 1,2-fashion (3, 6, 12-14, †) (Fig. 1). Finally, apolar olefins (e.g., α-olefins) commonly afford mixtures of both insertion modes in palladium-catalyzed Mizoroki-Heck (15) and polymerization reactions (16), whereas closely related nickel-catalyzed polymerizations of α-olefins can proceed with high selectivity by 1,2-insertion (17)-e.g., under kinetically controlled low-temperature conditions when sterically demanding ligands coordinate to nickel (16,18).The accepted rationale for these reactivity patterns is that electronic effects govern the regiochemistry of insertion for polarized carbon-carbon double bond substrates: In the Cossée-Arlman-type insertion step, the metal-bound, nucleophilic carbon atom migrates to the lower electron-density carbon atom of the double bond, while the electrophilic palladium atom migrates to the higher electron-density carbon atom of the double bond. In contrast, the insertion regiochemistry of apolar carbon-carbon double bonds is rather determined by steric effects (given that there is little electronic discrimination of the two olefinic carbon atoms), and under strict kinetic control the 1,2-insertion mode may preva...

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“…In our initial experiments, we chose the addition of styrene to 4-bromotoluene as a model reaction using Pd(OAc) 2 C; run time 25 min; inject 1.0 µL; helium as the GLC carrier gas; pressure of the system was 3.5 bar.…”

Section: Typical Experimental Proceduresmentioning

confidence: 99%