Organocatalytic Asymmetric Michael-Hemiacetalization Reaction Between 2-Hydroxyacetophenones and Enals: A Route to Chiral β,γ-Disubstituted γ-Butyrolactones

Balha, Megha; Mondal, Buddhadeb; Pan, Subhas Chandra

doi:10.1021/acs.joc.7b00363

Cited by 9 publications

(2 citation statements)

References 48 publications

(38 reference statements)

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“…α-Hydroxy ketones are important compounds used to synthesize a series of natural products and pharmaceuticals − in the field of organic chemistry. Among these compounds, 2-hydroxyacetophenone (2-HAP) is a promising and cost-effective synthetic intermediate widely used as a building block for the synthesis of valuable larger molecules, such as α-ketoesters, syn -amino alcohols, and antitumor Schiff bases. ,− Additionally, 2-HAP is used to prepare optically pure chemicals, such as ( R )- and ( S )-1-phenyl-1,2-ethanediol, which can be used as medicine intermediates and liquid crystal materials, respectively. , …”

Section: Introductionmentioning

confidence: 99%

One-Pot Enzymatic–Chemical Cascade Route for Synthesizing Aromatic α-Hydroxy Ketones

et al. 2021

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2-Hydroxyacetophenone (2-HAP) is an important building block for the production of a series of natural products and pharmaceuticals; however, there is no safe, efficient, and economical method for 2-HAP synthesis. Here, a one-pot enzymatic-chemical cascade route was designed for synthesizing 2-HAP based on retrosynthetic analysis. First, a spontaneous proton-transfer reaction was designed using a computational simulation that enabled 2-HAP synthesis from the isomer 2-hydroxy-2-phenylacetaldehyde. A route for 2-hydroxy-2-phenylacetaldehyde synthesis was then constructed by introducing the unnatural substrate glyoxylic acid into a C–C ligation reaction catalyzed by Candida tropicalis pyruvate decarboxylase. Assembly and optimization of this enzymatic–chemical cascade route resulted in a final yield of 92.7%. Furthermore, stereospecific carbonyl reductases were introduced to construct a synthetic application platform that enabled further transformation of 2-HAP into (S)- and (R)-1-phenyl-1,2-ethanediol. This method of cascading spontaneous chemical and enzymatic reactions to synthesize chemicals offers insight into avenues for synthesizing other valuable chemicals.

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Section: Introductionmentioning

confidence: 99%

One-Pot Enzymatic–Chemical Cascade Route for Synthesizing Aromatic α-Hydroxy Ketones

et al. 2021

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“…One of the most studied substrates in electron-deficient iminium ion catalysis to facilitate reactivity toward nucleophiles is α,β-unsaturated aldehydes because of their versatility derived from their easy transformation into electrophilic species with diarylprolinol silyl ethers . To further expand the scope of iminium ion catalysis, various catalytic domino or cascade transformations have been achieved through diarylprolinol silyl ether-catalyzed α,β-unsaturated aldehydes activation, such as the cascade Michael-aldol condensation, Michael–Michael reactions, Michael–Henry reactions, Michael–Morita–Baylis–Hillman reactions, multicomponent Michael-amination reactions, and so forth . It is clear that uncovering new reactivity and stereocontrol by classical iminium ion activation concept originated from condensation diarylprolinol silyl ethers and α,β-unsaturated aldehydes will benefit new domino reaction discoveries.…”

Section: Introductionmentioning

confidence: 99%

Organocatalytic Asymmetric Domino Oxa-Michael–Mannich-[1,3]-Amino Rearrangement Reaction of N-Tosylsalicylimines to α,β-Unsaturated Aldehydes by Diarylprolinol Silyl Ethers

Wang

Huang

et al. 2019

J. Org. Chem.

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An organocatalytic asymmetric enantioselective domino oxa-Michael–Mannich-[1,3]-amino rearrangement reaction of N-tosylsalicylimines with a wide range of α,β-unsaturated aldehydes utilizing diarylprolinol silyl ether catalysis is described. The catalytic reactions proceed with excellent enantioselectivity (up to 99% ee) to produce the corresponding chair N-tosylimines-chromenes with a yield of up to 99%, tolerating a range of functional groups. This methodology offers a new method with great potential to further extend the synthetic power and versatility of chiral aminocatalysis.

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Direct Organocatalytic Multicomponent Synthesis of Enantiopure γ‐Butyrolactones via Tandem Knoevenagel‐Michael‐Lactonization Sequence

et al. 2017

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An expedient and straightforward protocol is developed for the synthesis of highly enantiopure synthesis of γ‐butyrolactones. For the first time, one pot enantioselective organocatalytic multicomponent reaction (OMCR) is explored to construct functionalized butyrolactones without the use of pre‐functionalized substrates and expensive transition metals. The protocol is proved to be reproducible on a gram scale. Density functional theory (DFT) calculations strongly support the mechanism and were in close agreement with the observed high stereoselectivity.magnified image

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Organocatalytic Asymmetric Michael-Hemiacetalization Reaction Between 2-Hydroxyacetophenones and Enals: A Route to Chiral β,γ-Disubstituted γ-Butyrolactones

Cited by 9 publications

References 48 publications

One-Pot Enzymatic–Chemical Cascade Route for Synthesizing Aromatic α-Hydroxy Ketones

One-Pot Enzymatic–Chemical Cascade Route for Synthesizing Aromatic α-Hydroxy Ketones

Organocatalytic Asymmetric Domino Oxa-Michael–Mannich-[1,3]-Amino Rearrangement Reaction of N-Tosylsalicylimines to α,β-Unsaturated Aldehydes by Diarylprolinol Silyl Ethers

Direct Organocatalytic Multicomponent Synthesis of Enantiopure γ‐Butyrolactones via Tandem Knoevenagel‐Michael‐Lactonization Sequence

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