Practical Synthesis of both Enantiomeric Amino Acid, Mannich, and Aldol Derivatives by Asymmetric Organocatalysis

Liu, Yan; Arumugam, Natarajan; Almansour, Abdulrahman I.; Kumar, Raju Suresh; Maruoka, Keiji

doi:10.1002/tcr.201700008

Cited by 13 publications

(7 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In continuation of our interest in asymmetric synthesis of name reactions, [16–26] in this review, we wish to highlight the recent developments achieved and reported in asymmetric Mannich reaction. It is worthy to mention that the application of asymmetric organocatalyzed‐Mannich reaction in the total synthesis of naturally occurring compounds and heterocycles as power tool, has been extensively reviewed [4,27–43] …”

Section: Introductionmentioning

confidence: 99%

Organocatalyzed Asymmetric Mannich Reaction: An Update

et al. 2021

View full text Add to dashboard Cite

The Mannich reaction is a multicomponent reaction resulting in aminoalkylation of an acidic proton placed next to a carbonyl functional group. It involves an appropriate carbonyl compound, such as formaldehyde and a primary or secondary amine or ammonia. The final product is a β‐amino‐carbonyl compound known as a Mannich base. Reactions between aldimines and α‐methylene carbonyls are also considered as Mannich reaction since these imines are generated from the reaction of amines and aldehydes. It comprises the reaction of primary or secondary amines or ammonia, formaldehyde and appropriate α‐CH‐acidic compounds (nucleophiles) such as carbonyl compounds having α‐CH‐acidic, nitriles, acetylenes, aliphatic nitro compounds, α‐alkyl‐pyridines or imines. Owing to the development of asymmetric organocatalysis, reports on asymmetric Mannich reaction have been drastically increased. The asymmetric Mannich reaction offers access to enantioenriched β‐amino ketones or β‐amino aldehydes, which are present as a scaffold in several natural products. Organocatalysts have been developed not only as a supplement to metal‐catalyzed reactions or to biocatalysis, but nowadays, they are extensively used for the synthesis of various optically pure compounds that could not be achieved via metal‐ or biocatalyzed reactions. In this review, we try to update the advances in organocatalyzed asymmetric Mannich reactions, covering the recent advances of the subject from 2008 to date.

show abstract

Section: Introductionmentioning

confidence: 99%

Organocatalyzed Asymmetric Mannich Reaction: An Update

et al. 2021

View full text Add to dashboard Cite

show abstract

“…A quintessential example of stabilized 2-azaallyl anions is the benzophenone imine glycinate ester enolates popularized by O’Donnell and employed by several others (Scheme ). − In this particular circumstance, it is more appropriate to consider the anionic species as an α-iminoenolate given that the electron density is focused mostly on the enolate oxygen and not the 2-azaallyl framework. Such stabilized 2-azaallyl anions and their role in organic synthesis (particularly in relationship to phase-transfer catalysis) are summarized regularly ,− and, thus, will receive very little attention in this review.…”

Section: Introductionmentioning

confidence: 99%

“… − In this particular circumstance, it is more appropriate to consider the anionic species as an α-iminoenolate given that the electron density is focused mostly on the enolate oxygen and not the 2-azaallyl framework. Such stabilized 2-azaallyl anions and their role in organic synthesis (particularly in relationship to phase-transfer catalysis) are summarized regularly ,− and, thus, will receive very little attention in this review. Similarly, the related cyclic aromatic azlactone-derived oxazoline anions and their use in organic synthesis will not be addressed in this review .…”

Section: Introductionmentioning

confidence: 99%

2-Azaallyl Anions, 2-Azaallyl Cations, 2-Azaallyl Radicals, and Azomethine Ylides

et al. 2018

View full text Add to dashboard Cite

This review covers the use of 2-azaallyl anions, 2-azaallyl cations, and 2-azaallyl radicals in organic synthesis up through June 2018. Particular attention is paid to both foundational studies and recent advances over the past decade involving semistabilized and nonstabilized 2-azaallyl anions as key intermediates in various carbon–carbon and carbon–heteroatom bond-forming processes. Both transition-metal-catalyzed and transition-metal-free transformations are covered. Azomethine ylides, which have received significant attention elsewhere, are discussed briefly with the primary focus on critical comparisons with 2-azaallyl anions in regard to generation and use.

show abstract

“…Except for the aldol addition, the direct catalytic asymmetric α-functionalization of N-unprotected glycine derivatives has never been disclosed. An alternative method is the utilization of N-protect glycine derivatives, such as imino esters, as reactants . So, the development of novel chiral aldehyde catalysts and aldehyde catalyzed direct asymmetric α-functionalization of amino acids show good potential for applications in chiral aldehyde catalysis and amino acid chemistry.…”

Section: Introductionmentioning

confidence: 99%

Chiral Aldehyde Catalysis for the Catalytic Asymmetric Activation of Glycine Esters

et al. 2018

View full text Add to dashboard Cite

Chiral aldehyde catalysis is uniquely suitable for the direct asymmetric α-functionalization of N-unprotected amino acids, because aldehydes can reversibly form imines. However, there have been few successful reports of these transformations. In fact, only chiral aldehyde catalyzed aldol reactions of amino acids and alkylation of 2-amino malonates have been reported with good chiral induction. Here, we report a novel type of chiral aldehyde catalyst based on face control of the enolate intermediates. The resulting chiral aldehyde is the first efficient nonpyridoxal-dependent catalyst that can promote the direct asymmetric α-functionalization of N-unprotected glycine esters. Possible transition states and the proton transfer process were investigated by density functional theory calculations.

show abstract

Practical Synthesis of both Enantiomeric Amino Acid, Mannich, and Aldol Derivatives by Asymmetric Organocatalysis

Cited by 13 publications

References 36 publications

Organocatalyzed Asymmetric Mannich Reaction: An Update

Organocatalyzed Asymmetric Mannich Reaction: An Update

2-Azaallyl Anions, 2-Azaallyl Cations, 2-Azaallyl Radicals, and Azomethine Ylides

Chiral Aldehyde Catalysis for the Catalytic Asymmetric Activation of Glycine Esters

Contact Info

Product

Resources

About