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. 2020 Aug 7;10(15):8535-8541.
doi: 10.1021/acscatal.0c02607. Epub 2020 Jul 16.

Enantioselective, Aerobic Copper-Catalyzed Intramolecular Carboamination and Carboetherification of Unactivated Alkenes

Tomasz Wdowik  1 , Samuel L Galster  1 , Raul L L Carmo  1 , Sherry R Chemler  1
Affiliations

Enantioselective, Aerobic Copper-Catalyzed Intramolecular Carboamination and Carboetherification of Unactivated Alkenes

Tomasz Wdowik et al. ACS Catal. .

Abstract

Reduction of waste is an important goal of modern organic synthesis. We report herein oxidase reactivity for enantioselective intramolecular copper-catalyzed alkene carboamination and carboetherification reactions where previously used stoichiometric MnO2 has been replaced with oxygen. This substitution was risky as the reaction mechanism is thought to involve C-C bond formation via addition of alkyl carbon radicals to arenes. Such intermediates are also susceptible to C-O bond formation via O2 addition. Control of absolute stereochemistry under aerobic conditions was also uncertain. The oxidative cyclization efficiencies appear to track with the ease of the radical addition to the arenes.

Keywords: aerobic oxidation; alkene; asymmetric catalysis; carboamination; carboetherification; copper.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1.
Figure 1.
Bis(oxazoline) ligands used in this study.
Chart 1.
Chart 1.. Reaction Scope of Aerobic Enantioselective Carboamination of N-(4-Pentenyl)arylsulfonamidesa
aConditions from Table 2, entry 7 were used. TBS = tertbutyldimethylsilyl.
Chart 2.
Chart 2.. Reaction Scope of Aerobic Enantioselective Carboetherification of Alkenolsa
aConditions: Table 3, entry 10. bL6 was used.
Chart 3.
Chart 3.. Reaction Scope of Aerobic Enantioselective Spirocyclization of Alkenolsa
aConditions: Table 4, entry 9
Scheme 1.
Scheme 1.. Copper-Catalyzed Difunctionalization of Alkenes
aAr = aryl.
See this image and copyright information in PMC

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