Catalytic asymmetric Henry reaction

Boruwa, Joshodeep; Gogoi, Naminita; Saikia, Priyam; Barua, Nabin C.

doi:10.1016/j.tetasy.2006.12.005

Cited by 420 publications

(119 citation statements)

References 57 publications

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“…[3] Thesep rocesses represent two potent strategies for the synthesis of valuable b-hydroxy ketones and b-nitro alcohols providing, afterf urthert ransformations,e fficienta ccess to interesting and highly functionalized intermediates.B oth reactions have been developed under manyd ifferent conditions and using diverse catalytic systems,p roviding from good to excellent enantioselectivities. [4][5][6] During the development of our previous Henry protocol, [7] we realized that the presenceo ft races of acid in the aldehydes used could inactivate the small amount of catalyst employed (0.0044 mmol). It is well known that traces of acids are generatedi na ldehydes due to oxidation processes (see the Supporting Information for images of this process,F igure S1).…”

Section: Introductionmentioning

confidence: 99%

Organocatalyzed Enantioselective Aldol and Henry Reactions Starting from Benzylic Alcohols

2017

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Pioneering aldol and Henry reactions starting from benzylic-type alcohols are described. The aldol reactionh as been successfully performed following ao ne-pot strategys tarting from alcohols, while the Henry reaction has been carried out following as equential protocol for the first time.I n both processes, enantiomerically enriched products were obtainedw ith good yields and high enantioselectivities.W eh ave also demonstrated that in reactions sensitive to small amounts of acid the use of alcohols instead of aldehydes could be ag ood solution for improving the results of these reactions.

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Section: Introductionmentioning

confidence: 99%

Organocatalyzed Enantioselective Aldol and Henry Reactions Starting from Benzylic Alcohols

2017

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“…[9][10][11] With the optimized solvents in hand, the effect of temperature on enantioselectivity in the Henry reaction is also studied in a mixed protic solvent (EtOH/H 2 O, 3:1, v/v). The results from the different temperatures (Table 1) showed the enantioselectivity can not be further improved by lowering the temperature at the accompanying expense of increasing the reaction time.…”

Section: Synthesis Of No-type Inherently Chiral Calixmentioning

confidence: 99%

“…The resulting nitro alcohol (nitroaldol) products can be transformed into a number of nitrogen and oxygen-containing derivatives such as 1,2-amino alcohols, amino sugars, nitro ketones, nitro alkenes, ketones, and other important compounds. [9][10][11][12][13][14] It was reported that chiral N,O-type cupreidine derivatives can perform outstanding catalytical activities for Henry reaction. Mechanistic studies on their catalytic behaviors indicated they serve as acid-base bifunctional organocatalysts through H-bond interactions with the acceptor and donor components of the reactions through the quinuclidine nitrogen and the aromatic hydroxyl, respectively.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of N,O-Type Inherently Chiral Calix[4]arenes Substituted on the Lower Rim and their Organocatalysis Properties

Chang¹,

He²,

Zhou³

et al. 2016

J. Braz. Chem. Soc.

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This work presented the first study of organocatalytic behaviors of inherently chiral calix [4] arenes substituted at the lower rim. A pair of N,O-type enantiomers based on inherently chiral calix [4]arenes substituted at the lower rim were readily synthesized and applied to catalyze Henry reaction between aromatic aldehydes and nitromethane. Their organocatalytic reaction can afford the desired products in excellent yields (up to 99%) but poor enantioselectivities (up to 7.5% ee).

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“…anti-Selective Catalytic Asymmetric Nitroaldol (Henry) Reaction The nitroaldol (Henry) reaction is a valuable and robust methodology for carbon-carbon bondforming reactions that proceed under proton transfer conditions with perfect atom economy (Chart 4). [40][41][42][43] Almost 100 years have passed since the discovery of the transformation before the reaction was rendered enantioselective in a catalytic manner in 1992 using a LaLi 3 (binaphthoxide) 3 (LLB) catalyst. 44) Since then, catalytic asymmetric nitroaldol reactions have emerged as a useful protocol for the rapid assembly of enantioenriched 1,2-nitro alkanols, which allows for direct access to synthetically versatile 1,2-amino alcohols.…”

Section: Catalytic Asymmetric Amination Of Succinimide Derivatives mentioning

confidence: 99%

Development of Atom-Economical Catalytic Asymmetric Reactions under Proton Transfer Conditions: Construction of Tetrasubstituted Stereogenic Centers and Their Application to Therapeutics

Kumagai

2011

CHEMICAL & PHARMACEUTICAL BULLETIN

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The development of atom-economical catalytic asymmetric reactions based on two distinct sets of catalyst, a rare earth metal/amide-based ligand catalyst and a soft Lewis acid/hard Brønsted base catalyst, is reviewed. These catalytic systems exhibit high catalytic activity and stereoselectivity by harnessing a cooperative catalysis through hydrogen bond/metal coordination and soft-soft interactions/hard-hard interactions, respectively. The effectiveness of these cooperative catalysts is clearly delineated by the high stereoselectivity in reactions with highly coordinative substrates, and the specific activation of otherwise low-reactive pronucleophiles under proton transfer conditions. The rare earth metal/amide-based ligand catalyst was successfully applied to catalytic asymmetric aminations, nitroaldol (Henry) reactions, Mannich-type reactions, and conjugate addition reactions, generating stereogenic tetrasubstituted centers. Catalytic asymmetric amination and anti-selective catalytic asymmetric nitroaldol reactions were successfully applied to the efficient enantioselective synthesis of therapeutic candidates, such as AS-3201 and the b b 3 -adrenoreceptor agonist, showcasing the practical utility of the present protocols. The soft Lewis acid/hard Brønsted base cooperative catalyst was specifically developed for the chemoselective activation of soft Lewis basic allylic cyanides and thioamides, which are otherwise low-reactive pronucleophiles. The cooperative action of the catalyst allowed for efficient catalytic generation of active carbon nucleophiles in situ, which were integrated into subsequent enantioselective additions to carbonyl-type electrophiles.

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Catalytic asymmetric Henry reaction

Cited by 420 publications

References 57 publications

Organocatalyzed Enantioselective Aldol and Henry Reactions Starting from Benzylic Alcohols

Organocatalyzed Enantioselective Aldol and Henry Reactions Starting from Benzylic Alcohols

Synthesis of N,O-Type Inherently Chiral Calix[4]arenes Substituted on the Lower Rim and their Organocatalysis Properties

Development of Atom-Economical Catalytic Asymmetric Reactions under Proton Transfer Conditions: Construction of Tetrasubstituted Stereogenic Centers and Their Application to Therapeutics

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