Visible Light Induced Copper‐Catalyzed Enantioselective Deaminative Arylation of Amino Acid Derivatives Assisted by Phenol

Abstract

The exploration of value‐added conversions of naturally abundant amino acids has received considerable attention from the synthetic community. Compared with the well‐established asymmetric decarboxylative transformation, the asymmetric deaminative transformation of amino acids still remains a formidable challenge, mainly due to the lack of effective strategies for the C−N bond activation and the potential incompatibility with chiral catalysts. Here, we disclose a photoinduced Cu‐catalyzed asymmetric deaminative coupling reaction of amino acids with arylboronic acids. This new protocol provides a series of significant chiral phenylacetamides in generally good yields and excellent stereoselectivity under mild and green conditions (42–85 % yields, up to 97 % ee). Experimental investigations and theoretical calculations were performed to reveal the crucial role of additional phenols in improving catalytic efficiency and enantiocontrol.

Hydrogen Bonding-Induced Aggregation of Chiral Functionalized AuNS@Ag NPs for Photothermal Enantioanalysis

“…5−7 Although many specific physiological functions are still being investigated, Damino acids have garnered increasing attention as potential disease markers and for the treatment of neurological disorders, such as schizophrenia, Parkinsonism syndrome, and Alzheimer's disease. 8−10 Additionally, the structural diversity of naturally occurring amino acids has found extensive applications in the chemical industry 11,12 and pharmaceutical sciences. 13−15 Two types of enantiomers have become inestimable initial ingredient for the stereoselective synthesis of physiological activators and novel functional materials.…”

“…The stereoisomeric recognition of biomolecules in nature exhibits a noteworthy level of specificity, resulting in two mirror image permutations of enantiomers that elicit quite different biological reactions. , In this context, chiral amino acids play a crucial role in various metabolic processes and serve as indispensable building blocks for proteins and other biomolecules. , In recent years, there has been a shift in emphasis from proteogenic l -amino acids to the emerging biological significance of several d -antipodes. Free d -amino acids have been unveiled to play crucial biological and pathological roles in living organisms. − Although many specific physiological functions are still being investigated, d -amino acids have garnered increasing attention as potential disease markers and for the treatment of neurological disorders, such as schizophrenia, Parkinsonism syndrome, and Alzheimer’s disease. − Additionally, the structural diversity of naturally occurring amino acids has found extensive applications in the chemical industry , and pharmaceutical sciences. − Two types of enantiomers have become inestimable initial ingredient for the stereoselective synthesis of physiological activators and novel functional materials . Consequently, the exploitation of sensitive and accessible analytical techniques to discriminate between enantiomers of amino acids is extraordinarily attractive and challenging.…”

Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis

“…Alongside the traditional asymmetric cyclopropanation reactions of alkenes, the asymmetric transformation of cyclopropenes has been gradually developed, often using organometallic reagents as the starting materials . Inspired by these remarkable studies and our recent focus on AMPC-enabled asymmetric photochemical synthesis, − , we hypothesized that this approach could be extended to the desymmetrization–addition reaction of cyclopropenes to imines, thus providing access to chiral amines with a cyclopropane core (Figure d). Potential challenges of this strategy include 1) simultaneous stereocontrol of multiple consecutive stereogenic centers, including a chiral all-carbon quaternary stereocenter, 2) recognition of the symmetric CC double bond of cyclopropenes without a directing group, and 3) competitive processes such as the reductive hydrogenation of imines and cyclopropenes and the homocoupling of imines …”