Recent Advances in Intermolecular Hydroacylation of Alkenes with Aldehydes through Rhodium Catalysis

Guo, Rui; Zhang, Guozhu

doi:10.1055/s-0037-1610141

Cited by 22 publications

(1 citation statement)

References 8 publications

(7 reference statements)

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“…The hydroacylation of a variety of unsaturated hydrocarbons with chelating or non‐chelating aldehydes by virtue of the formyl C( sp 2 )−H bond activation is one of the most valuable chemical transformations for the construction of carbonyl compounds [1–10] . Consequently, considerable research interests have been attracted to olefin and carbonyl hydroacylation in pursuing the highly efficient and completely atom‐economical synthesis (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Rhodium(I) Catalyzed Hydroacylation Reactions of Alkenyl Compounds

Zhao,

Lu,

Wang

et al. 2024

Adv Synth Catal

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Transition‐metal‐catalyzed hydroacylation of unsaturated substrates with aldehydes involving the formyl C(sp2)–H bond activation provides an expedient and efficient access to the carbonyl compounds such as ketones and esters, which are a class of important scaffolds in natural products and in drug development. Recently, extensive attention has been paid to the hydroacylation reactions of the components containing an alkenyl moiety that can trigger a regioselective transformation in the presence of a transition metal catalyst. In this review, we summarize the constructive endeavors in rhodium(I)‐catalyzed (formal) hydroacylation reactions from 2018, and the plausible pathway is also dissected to offer some insights into the reaction mechanism.

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Section: Introductionmentioning

confidence: 99%

Rhodium(I) Catalyzed Hydroacylation Reactions of Alkenyl Compounds

Zhao,

Lu,

Wang

et al. 2024

Adv Synth Catal

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The Catalytic Enantioselective Stetter Reaction

Flanigan¹,

Ozboya²,

Tanpure³

et al. 2021

Organic Reactions

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The catalytic enantioselective Stetter reaction is the coupling of an aldehyde with an electron‐deficient alkene via the conjugate addition of an acyl anion equivalent (Breslow intermediate) generated from the aldehyde and a chiral N ‐heterocyclic carbene (NHC) catalyst. The process affords 1,4‐dicarbonyl compounds and related systems, such as β‐nitroketones, in an efficient and atom‐economical fashion and with generally good‐to‐excellent enantioselectivities when fused polycyclic chiral triazolylidenes are employed as the NHC catalysts. The scope of the transformation is particularly broad for intramolecular reactions, but in the case of the intermolecular variant, only certain types of aldehyde donors and electrophilic alkenes can be successfully coupled together. This chapter describes theoretical and operational aspects of the catalytic enantioselective Stetter reaction such that the reader will be able to obtain optimal results in their own research. A detailed mechanistic overview is included to account for the factors that influence stereoselectivity and yield, and results from experimental and computational mechanistic studies are summarized. In addition, catalyst synthesis, reaction variants, applications in target‐directed synthesis, and comparison to other methods for generating 1,4‐dicarbonyl compounds are also presented. Tabular surveys are organized according to the modality of reactivity, either intra‐ or intermolecular, and the type of aldehyde donor. The literature is covered from the first disclosure of a catalytic enantioselective Stetter reaction in 1996 through to the end of 2019.

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Direct Carbohydroxylation of Arylalkenes with Allylic Alcohols: Cooperative Catalysis of Copper, Silver, and a Brønsted Acid

Ahmed

Zhang

et al. 2019

Angewandte Chemie

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The cooperative catalysis of copper,s ilver,a nd Brønsted acid is presented as an ew strategy for olefin functionalization. The catalytic direct carbohydroxylation of arylalkenes with allylic alcohols provided as traightforward and efficient approach for preparing 4,5-unsaturated alcohols. Synthetically useful functional groups,such as Cl, Br,carbonyl, and chloromethyl, remained intact during the functionalization reaction.The transition metal catalyzed functionalization of olefins is ap owerful tool to convert readily available petrochemical feedstocks into valuable synthetic building blocks. [1] The development of convenient and efficient methods for the functionalization of olefins is still ar esearch hotspot in organic synthesis although many catalytic methods for the mono-and di-functionalization of olefins have been reported over the past years.Many kind of metals,such as palladium, [2] rhodium, [3] gold, [4] nickel, [5] and copper, [6] were employed as the catalysts for this purpose.Direct carbohydroxylation of alkenes,w hich is the addition of C( alkyl and aryl) and OH to alkenes,i sa n important synthetic method for functionalization of the C=C bond. However,tothe best of our knowledge,only few papers on direct carbohydroxylation, namely arylhydroxylation of alkenes,h ave been reported, and they involve ar adical process. [7] Some examples of indirect carbohydroxylation of alkenes are known. [8] In addition, catalytic allylation of olefins,aH eck-type coupling reaction using allylic ethers, [9] allylic carbonates, [9] allylic tosylate, [10] and allylic alcohols [11] as allyl sources have also been reported. However,a sf ar as we know,t here is no precedent of direct addition of allylic alcohols to alkenes using transition-metal catalysts.H erein, we report that aw ide range of arylalkenes react with allylic alcohols under the cooperative catalysis of Cu, Ag, and[*] W. Ahmed, [+] Dr.

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Recent Advances in Intermolecular Hydroacylation of Alkenes with Aldehydes through Rhodium Catalysis

Cited by 22 publications

References 8 publications

Rhodium(I) Catalyzed Hydroacylation Reactions of Alkenyl Compounds

Rhodium(I) Catalyzed Hydroacylation Reactions of Alkenyl Compounds

The Catalytic Enantioselective Stetter Reaction

Direct Carbohydroxylation of Arylalkenes with Allylic Alcohols: Cooperative Catalysis of Copper, Silver, and a Brønsted Acid

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