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J Am Chem Soc. 2019 Apr 24;141(16):6698-6705. doi: 10.1021/jacs.9b01911. Epub 2019 Apr 10.

Disparate Catalytic Scaffolds for Atroposelective Cyclodehydration.

Author information

1
Department of Chemistry , Yale University , New Haven , Connecticut 06520-8107 , United States.
2
Department of Chemistry , University of California, Berkeley , Berkeley , California 94720 , United States.
3
Department of Chemistry , University of Utah , 315 South 1400 East , Salt Lake City , Utah 84112 , United States.

Abstract

Catalysts that control stereochemistry are prized tools in chemical synthesis. When an effective catalyst is found, it is often explored for other types of reactions, frequently under the auspices of different mechanisms. As successes mount, a unique catalyst scaffold may become viewed as "privileged". However, the mechanistic hallmarks of privileged catalysts are not easily enumerated or readily generalized to genuinely different classes of reactions or substrates. We explored the concept of scaffold uniqueness with two catalyst types for an unusual atropisomer-selective cyclodehydration: (a) C2-symmetric chiral phosphoric acids and (b) phosphothreonine-embedded, peptidic phosphoric acids. Pragmatically, both catalyst scaffolds proved fertile for enantioselective/atroposelective cyclodehydrations. Mechanistic studies revealed that the determinants of often equivalent and high atroposelectivity are different for the two catalyst classes. A data-descriptive classification of these asymmetric catalysts reveals an increasingly broad set of catalyst chemotypes, operating with different mechanistic features, that creates new opportunities for broad and complementary application of catalyst scaffolds in diverse substrate space.

PMID:
30920223
PMCID:
PMC6482060
[Available on 2020-04-24]
DOI:
10.1021/jacs.9b01911

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