The role of zinc carbenoids in organic synthesis

Motherwell, W. B.; Nutley, C. J.

doi:10.1039/co9940100219

Cited by 46 publications

(18 citation statements)

References 74 publications

(7 reference statements)

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“…[2] One approach to addressing this problem is to prioritize lead compounds that contain higher fractions of sp 3 -hybridized carbons. [5,6] An alterna-tive disconnection that could be considered is the addition of a cyclic carbene to an alkene. [4] Spirocyclopropanes may be prepared by the addition of a carbene equivalent to a methylenecycloalkane.…”

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confidence: 99%

“…[4] Spirocyclopropanes may be prepared by the addition of a carbene equivalent to a methylenecycloalkane. [5,6] An alterna-tive disconnection that could be considered is the addition of a cyclic carbene to an alkene. Recently, Charette demonstrated the generation of sensitive diazocycloalkanes in flow reactors and their uncatalyzed addition to α,β-unsaturated esters.…”

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confidence: 99%

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Cobalt Catalyzed Reductive Spirocyclopropanation Reactions

2019

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Cobalt pyridineÀ diimine (PDI) complexes catalyze the reductive spirocyclopropanation of terminal 1,3-dienes. gem-Dichlorocycloalkanes serve as carbene precursors and Zn is used as a terminal electron source. The reaction is effective for a range of gem-dichloro partners including those containing sulfur and nitrogen heterocycles. An example of an intramolecular Rh-catalyzed [5 + 2]cycloaddition of a vinyl spirocyclopropane is demonstrated, providing rapid access to a complex tricyclic framework. Overall, this catalyst system is capable of suppressing the kinetically facile 1,2hydride shift, which has hampered the development of SimmonsÀ Smith reactions using Zn carbenoids possessing β-hydrogen atoms.

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confidence: 99%

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confidence: 99%

Cobalt Catalyzed Reductive Spirocyclopropanation Reactions

2019

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“…On the other hand, the formation of alkanes and alkenes by hydrogenation and deoxygenation, respectively, of sterically hindered ketones in McMurry reactions is reminiscent of the Clemmensen reaction, that is the reduction of a carbonyl to a methylene group by means of zinc and hydrochloric acid [293], or its modified version, that is the synthesis of alkenes by deoxygenation of carbonyl compounds with zinc and chlorosilane [294][295][296]. These reactions, which were shown to involve zinc carbenoid intermediates resulting from reduction and deoxygenation of ketyl radicals, also produce a number of side products, in particular pinacols and coupled alkenes, which are the normal products of McMurry reactions; it has been demonstrated that the deoxygenative coupling process does not proceed via pinacol-type intermediates.…”

Section: Mechanistic Analogies Between the Mcmurry Wittig And Clemmmentioning

confidence: 99%

The McMurry Coupling and Related Reactions

Ephritikhine

Villiers

2003

Modern Carbonyl Olefination

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“…23 In the conventional Clemmensen reduction, zinc is typically used as a stoichiometric reductant. However, in cathodic Clemmensen-type reduction electrons are the reductant while zinc plays a catalytic role.…”

Section: Electrode Selectivity Requirementsmentioning

confidence: 99%

Towards selective electrochemical conversion of glycerol to 1,3-propanediol

James

Sauter²,

Schröder³

2018

RSC Adv.

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1,3-propanediol (1,3-PD) is a bulk chemical with myriad applications in polymers, lubricants, cosmetics, foods industries and in the synthesis of heterocyclic compounds. Current commercial production of 1,3-PD involves a thermocatalytic process using acrolein (DuPont) and ethylene oxide (Shell) as starting feedstock. These feedstocks are petroleum-based and there are many efforts at using glycerol as low cost biomass-derived feedstock for 1,3-PD production. A number of catalyst designs and bacterial & fungal strains are being explored for respective catalytic and fermentation routes to glycerol-to-1,3-PD.However, the electrochemical method received little attention for the purpose. In this work, in order to explore the possibility of using partly refined glycerol byproduct of biodiesel production as feedstock, we investigated conversion and 1,3-PD selectivity of glycerol electrolysis in chloride media. We demonstrated selective glycerol-to-1,3-PD conversion using Pt or RuO 2 -based dsa as anode and Zn or Pb as cathode in NaCl and KCl at pH 1. This electrochemical glycerol-to-1,3-PD conversion is not only green, it is a potential process network loop between biodiesel production and chlor-alkali industry.

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The role of zinc carbenoids in organic synthesis

Cited by 46 publications

References 74 publications

Cobalt Catalyzed Reductive Spirocyclopropanation Reactions

Cobalt Catalyzed Reductive Spirocyclopropanation Reactions

The McMurry Coupling and Related Reactions

Towards selective electrochemical conversion of glycerol to 1,3-propanediol

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