PtI4-catalyzed oxidative and hydrogenative dearomative [3+2] cycloaddition of 1H-indole N-tethered o-alkynylbenzaldehydes

A synthetic method for the chemodivergent assembly of a diverse range of highly functionalized and architecturally challenging cyclohepta[b]indolines which relies on PtI4-catalyzed oxidative and hydrogenative dearomative [3 + 2] cycloaddition of 1H-indole N-tethered o-alkynylbenzaldehydes in a singl...

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Published inORGANIC CHEMISTRY FRONTIERS Vol. 10; no. 1; pp. 140 - 149
Main Authors Shang, Dandan, Hu, Rui, Bao, Qing, Chen, Jichao, Yu, Lei, Chan, Philip Wai Hong, Rao, Weidong
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 01.01.2023
Royal Society of Chemistry
Subjects
Biological activity
Chemistry
Chemistry, Organic
Cycloaddition
Functional groups
Heterocyclic compounds
Natural products
Organic chemistry
Oxidation
Physical Sciences
Reagents
Science & Technology
Selectivity
INSERTION
BENZOPYRYLIUM
TANDEM
CONTAINING CARBONYL YLIDES
CONSTRUCTION
CATALYZED REACTION
GENERATION
INDOLE ALKALOIDS
CYCLIZATION
ACTINOPHYLLIC ACID
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Summary:A synthetic method for the chemodivergent assembly of a diverse range of highly functionalized and architecturally challenging cyclohepta[b]indolines which relies on PtI4-catalyzed oxidative and hydrogenative dearomative [3 + 2] cycloaddition of 1H-indole N-tethered o-alkynylbenzaldehydes in a single operation is described. For the synthesis of a key structural feature that is found in a myriad of bioactive natural products and pharmaceutical compounds, the proposed cascade chemodivergent process delineates the first example of an in situ formed Pt-bound benzopyrylium intermediate that participates in [3 + 2] cycloaddition with the C(2) 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 C(3) bond of an aromatic N-heterocycle as the 2 pi cycloaddition partner with exclusive exo-selectivity in a highly efficient manner. It also offers a unique instance of the resulting metallocarbene species generated in this manner undergoing either oxidation by phenylmethylsulfoxide or reduction by THF, with the solvent as both the hydride and alkyl reagent source. The chemodivergent protocol exhibits exceptional functional group tolerance and is amenable to the late-stage modification of a series of structurally complex bioactive natural products and drug molecules.
ISSN:2052-4129
2052-4110
2052-4110
DOI:10.1039/d2qo01520j