Enantioselective Cobalt‐Catalyzed Intermolecular Hydroacylation of 1,6‐Enynes

Whyte, Andrew; Bajohr, Jonathan; Torelli, Alexa; Lautens, Mark

doi:10.1002/anie.202006716

Cited by 47 publications

(13 citation statements)

References 65 publications

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“…From our initial studies, it appears that the published protocol for diene hydroacylation (CoI 2 /In/InBr 3 /DCE/60 °C) may not be suitable for enantioselective versions of several dienes, especially for the more substituted ones that are sensitive to Lewis acids (see later, Table and Table S1 in the Supporting Information). Yet another noteworthy example in the context of cobalt catalysis is Brookhart’s Cp*Co(I)(vinylsilane) 2 -catalyzed hydroacylation of vinylsilane. , In addition, a 1,6-enyne cycloisomerization terminating with a hydroacylation has been reported, and an enantioselective version of this reaction uses the catalyst system similar to what we first reported in 2017 . No examples of enantioselective hydroacylation of 1,3-dienes have been reported to date .…”

Section: Introductionmentioning

confidence: 90%

α- and β-Functionalized Ketones from 1,3-Dienes and Aldehydes: Control of Regio- and Enantioselectivity in Hydroacylation of 1,3-Dienes

Parsutkar

RajanBabu

2021

J. Am. Chem. Soc.

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Ketones are among the most widely used intermediates in organic synthesis, and their synthesis from inexpensive feedstocks could be quite impactful. Regio-and enantioselective hydroacylation reactions of dienes provide facile entry into useful ketone-bearing chiral motifs with an additional latent functionality (alkene) suitable for further elaboration. Three classes of dienes, 2-or 4-monosubstituted and 2,4-disubstituted 1,3-dienes, undergo cobalt(I)-catalyzed regio-and enantioselective hydroacylation, giving products with high enantiomeric ratios (er). These reactions are highly dependent on the ligands, and we have identified the most useful ligands and reaction conditions for each class of dienes. 2-Substituted and 2,4-disubstituted dienes predominantly undergo 1,2-addition, whereas 4-substituted terminal dienes give highly enantioselective 4,1-or 4,3-hydroacylation depending on the aldehyde, aliphatic aldehydes giving 4,1-addition and aromatic aldehydes giving 4,3-addition. Included among the substrates are feedstock dienes, isoprene (US$1.4/kg) and myrcene (US$129/kg), and several common aldehydes. We propose an oxidative dimerization mechanism that involves a Co(I)/Co(III) redox cycle that appears to be initiated by a cationic Co(I) intermediate. Studies of reactions using isolated neutral and cationic Co(I) complexes confirm the critical role of the cationic intermediates in these reactions. Enantioselective 1,2-hydroacylation of 2-trimethylsiloxy-1,3-diene reveals a hitherto undisclosed route to chiral siloxy-protected aldols. Finally, facile syntheses of the anti-inflammatory drug (S)-Flobufen (2 steps, 92% yield, >99:1 er) and the food additive (S)-Dihydrotagetone (1 step, 83% yield; 96:4 er) from isoprene illustrate the power of this method for the preparation of commercially relevant compounds.

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Section: Introductionmentioning

confidence: 90%

α- and β-Functionalized Ketones from 1,3-Dienes and Aldehydes: Control of Regio- and Enantioselectivity in Hydroacylation of 1,3-Dienes

Parsutkar

RajanBabu

2021

J. Am. Chem. Soc.

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“…图式 37 醛和酮酰胺的不对称氢酰化 Scheme 37 Asymmetric hydroacylation of ketoamides and aldehyde 2020 年, Lautens 等 [54]…”

Section: 过渡金属催化的不对称分子内氢酰化反应unclassified

Research Advance on Enantioselective Transition Metal-Catalyzed Hydroacylation Reactions

Wang¹,

Ye²

2022

Chinese Journal of Organic Chemistry

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Transition metal-catalyzed hydroacylation reaction of aldehydes with π-unsaturated compounds provides an economical and efficient method for the construction of C-C bonds, not only allowing readily available starting materials to be used as substrates, but also featuring high atom and step economy. Therefore, the reaction has received continuous and extensive attention during the past several decades. The advances on enantioselective transition metal-catalyzed hydroacylation reactions are summarized, focusing on reaction types, asymmetric strategies and reaction mechanisms.

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“…[11] Enantioenriched ketones were synthesized via hydroacylation of 1,6-enynes with aldehydes using CoBr 2 as catalyst, ligand (S,S)-BDPP, and NaBARF {natriumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate À } in the presence of zinc dust. [12] A range of aryl-substituted substrates was reacted to give chiral pyrrolidines in low to excellent yields with high enantiomeric ratios (Scheme 6). The lowest e.r.…”

Section: Cobalt-catalyzed Processesmentioning

confidence: 99%

Stereoselective Synthesis of Azacycles Induced by Group 8–11 Late Transition Metals

Molnár

2021

Eur J Org Chem

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The aim of the present minireview is to summarize and discuss recent advances in the field of stereoselective synthesis of azacycles. The focus is on studies that appeared in the last two years to illustrate recent trends with a handful of examples from 2019 highlighting an important field of enantioselective chemistry. Results collected and discussed here show that syntheses catalyzed by late transition metals of group 8-11 afford products in high yield with high stereoselectivity, often under mild reaction conditions thereby demonstrating their efficacy to afford valuable products. Plausible reaction mechanisms for most transformations are also discussed.

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Enantioselective Cobalt‐Catalyzed Intermolecular Hydroacylation of 1,6‐Enynes

Cited by 47 publications

References 65 publications

α- and β-Functionalized Ketones from 1,3-Dienes and Aldehydes: Control of Regio- and Enantioselectivity in Hydroacylation of 1,3-Dienes

α- and β-Functionalized Ketones from 1,3-Dienes and Aldehydes: Control of Regio- and Enantioselectivity in Hydroacylation of 1,3-Dienes

Research Advance on Enantioselective Transition Metal-Catalyzed Hydroacylation Reactions

Stereoselective Synthesis of Azacycles Induced by Group 8–11 Late Transition Metals

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