Kinetic Resolution of Hindered Morita–Baylis–Hillman Adducts by Rh(I)-Catalyzed Asymmetric 1,4-Addition/β-Hydroxyelimination

Wang, Yazhou; Feng, Xiujuan; Du, Haifeng

doi:10.1021/ol202069e

Cited by 55 publications

(14 citation statements)

References 71 publications

(15 reference statements)

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“…Kinetic resolution can be employed to obtain optically pure or enriched molecules therefrom. [20][21][22] The use of enzymes for the kinetic resolution of secondary carbinols is well documented, 23,24 and has proved to be economically and environmentally advantageous. Previous studies regarding biocatalytic resolution of enantiomers of 3(RS)-hydroxy-2-methylenebutanenitrile 1(RS) were focused on the optimization of transesterification reaction conditions using lipase from Pseudomonas cepacia.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, lipase catalyzed kinetic resolution, and determination of the absolute configuration of enantiomers of the Morita-Baylis-Hillman adduct 3-hydroxy-2-methylenebutanenitrile

Strub¹,

Garboś²,

Lochyński³

2016

Arkivoc

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3(RS)-Hydroxy-2-methylenebutanenitrile was synthesized from acetaldehyde and acrylonitrile with DABCO as a catalyst. Optimization of the reaction conditions was conducted because some literature procedures were not reproducible. Asymmetric transesterification of the Morita-Baylis-Hillman adduct was carried out using ten lipases. The hydroxyl-nitrile was also esterified chemically and subjected to enzymatic hydrolysis with the same set of enzymes. The best results were obtained with lipase from Candida antarctica and Novozyme 435. The absolute configuration of an optically pure hydroxyl-nitrile was determined by Mosher's method.

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Section: Introductionmentioning

confidence: 99%

Synthesis, lipase catalyzed kinetic resolution, and determination of the absolute configuration of enantiomers of the Morita-Baylis-Hillman adduct 3-hydroxy-2-methylenebutanenitrile

Strub¹,

Garboś²,

Lochyński³

2016

Arkivoc

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“…In the reactions using acrylamides and enamides, the coordination of the amide carbonyl into rhodium induce high reactivity and selectivity,a nd suppresst he undesired b-hydrogen elimination giving dienep roducts. [6, 7a, 9] In 2016, Roglans andP la-Quintana reported that racemic secondary allylic alcohols [10] react with 1,6-diynes through the kinetic resolution [11] in the presenceo facationic rhodium(I)/ binap complex to give bicyclic cyclohexadienes (Scheme 1b). [12] This reactionc an construct contiguous two stereogenic centers as as ingled iastereomer with high ee values, whilet he substrate scope was somewhat limited( methoxycarbonyl-and aryl-substituted allylic alcohols, ands ulfonamide-linked and dimethyl-substituted 1,6-diynes).Inthis Communication, we have established that ac ationic rhodium(I)/Pphos complex is capableo fc atalyzing the regio-,d iastereo-, and enantioselective [2+ +2+ +2] cycloaddition of 1,6-enynes with racemic secondary allylic alcohols through the kineticr esolution at room temperature giving chiralb icyclic cyclohexenes, possessing three stereogenic centers (Scheme 1c).…”

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confidence: 99%

Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition of 1,6‐Enynes with Racemic Secondary Allylic Alcohols through Kinetic Resolution

Suzuki

Shibata

Tanaka

2020

Chemistry A European J

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It has been established that a cationic rhodium(I)/P‐phos complex catalyzes the asymmetric [2+2+2] cycloaddition of 1,6‐enynes with racemic secondary allylic alcohols to produce the corresponding chiral bicyclic cyclohexenes, possessing three stereogenic centers, as a single diastereomer with excellent ee values. Mechanistic experiments revealed that the present cycloaddition proceeds through the kinetic resolution of the racemic secondary allylic alcohols, in which one enantiomer preferentially reacts with the 1,6‐enyne.

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“…[13,14] These studies demonstrated that simple and readily available chiral sulfur-olefin hybrid ligands can also display great catalytic activities and enantioselectivities in asymmetric catalysis. We have recently become intrigued by the possibility of their application in the more challenging enantioselective 1,2-addition of aryl boronic acids to more activated ketones, such as a-ketoesters and a-diketones, to provide optically active, functionalized tertiary alcohols.…”

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confidence: 99%

“…The catalytic asymmetric addition to a-diketones represents an unprecedented synthesis of optically active, tertiary a-hydroxyketone derivatives. Moreover, aside from their use in 1,4-addition to a,b-unsaturated carbonyl compounds, [13,14] this is the first example of the successful application of the recently developed, chiral sulfur-olefin ligands in asymmetric catalysis, wherein the unique sulfonamide-olefin 3 has been shown to be highly effective. It opens new opportunities for the use of this novel class of readily available ligands in related asymmetric processes.…”

mentioning

confidence: 99%

Rhodium‐Catalyzed, Highly Enantioselective 1,2‐Addition of Aryl Boronic Acids to α‐Ketoesters and α‐Diketones Using Simple, Chiral Sulfur–Olefin Ligands

2011

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Optically active a-hydroxy carbonyl compounds are not only very important structural motifs in numerous biologically interesting compounds, but also serve as fundamental building blocks for numerous applications in organic synthesis. [1] Over the past decades, various methods have been developed for the synthesis of these valuable chiral compounds. [2][3][4][5] Among these, the transition-metal-catalyzed asymmetric nucleophilic addition of organometallic reagents to a-keto carbonyl compounds is a particularly powerful and straightforward approach. [4] In recent years, the use of stable, commercially available aryl boronic acids in place of common organometallic reagents in transition-metal-catalyzed carbon-carbon bond-forming reactions has attracted considerable attention. [5,6] However, despite these successes with asymmetric reactions involving a,b-unsaturated carbonyl compounds [7] and aldimines, [8] the transition-metal-catalyzed asymmetric addition of aryl boronic acids to carbonoxygen double bonds in ketones (producing enantioenriched tertiary alcohols) remains under-studied and elusive. To date, only very limited progress has been achieved in the rhodiumcatalyzed asymmetric addition of these species to isatins (up to 91 % ee), [5a,b] a-ketoesters (up to 95 % ee), [5c,d, 9] and atrifluoromethyl ketones (up to 83 % ee);[10] all methods that employ chiral phosphine, phosphite, or phosphoramidite ligands.[11] With respect to a-diketones, to the best of our knowledge, there are no examples of their catalytic, enantioselective coupling with aryl boronic acids to provide optically active, tertiary a-hydroxyketones.[12] Thus, the development of new catalytic systems that are capable of the efficient synthesis of enantiomerically pure a-hydroxy carbonyl compounds with a quaternary stereogenic center is highly desirable.We have recently designed a series of chiral sulfinamide/ sulfoxide-based olefin ligands and successfully employed them in the rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to a,b-unsaturated carbonyl compounds. [13,14] These studies demonstrated that simple and readily available chiral sulfur-olefin hybrid ligands can also display great catalytic activities and enantioselectivities in asymmetric catalysis. We have recently become intrigued by the possibility of their application in the more challenging enantioselective 1,2-addition of aryl boronic acids to more activated ketones, such as a-ketoesters and a-diketones, to provide optically active, functionalized tertiary alcohols. Herein we describe our efforts to address this issue. By employing an extremely simple, chiral N-(sulfinyl)cinnamylamine as a ligand, aryl boronic acids were effectively activated under rhodium catalysis to react stereoselectively with both a-ketoesters and a-diketones, giving products with excellent enantioselectivities under exceptionally mild conditions.In our initial studies, we attempted to test whether our recently designed chiral sulfinamide/sulfoxide-olefins 1-3 can act as chiral ligands in the ...

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Kinetic Resolution of Hindered Morita–Baylis–Hillman Adducts by Rh(I)-Catalyzed Asymmetric 1,4-Addition/β-Hydroxyelimination

Cited by 55 publications

References 71 publications

Synthesis, lipase catalyzed kinetic resolution, and determination of the absolute configuration of enantiomers of the Morita-Baylis-Hillman adduct 3-hydroxy-2-methylenebutanenitrile

Synthesis, lipase catalyzed kinetic resolution, and determination of the absolute configuration of enantiomers of the Morita-Baylis-Hillman adduct 3-hydroxy-2-methylenebutanenitrile

Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition of 1,6‐Enynes with Racemic Secondary Allylic Alcohols through Kinetic Resolution

Rhodium‐Catalyzed, Highly Enantioselective 1,2‐Addition of Aryl Boronic Acids to α‐Ketoesters and α‐Diketones Using Simple, Chiral Sulfur–Olefin Ligands

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