Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group

Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group

Alkenes are the most ubiquitous pro-chiral functional groups accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes are particularly important, as they can be used to access highly complex molecular architectures.1,2 Stereoselective oxidation reactions, including...

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Main Authors: Piou, Tiffany, Rovis, Tomislav
Format: Online
Language:English
Published: 2015
Online Access:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4636455/
id pubmed-4636455
recordtype oai_dc
spelling pubmed-46364552016-05-05 Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group Piou, Tiffany Rovis, Tomislav Article Alkenes are the most ubiquitous pro-chiral functional groups accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes are particularly important, as they can be used to access highly complex molecular architectures.1,2 Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation reactions,3,4,5,6 are well-established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. In this manuscript, we describe the Rh(III)-catalyzed syn carboamination of alkenes initiated by a C–H activation event that uses enoxyphthalimides as the source of the carbon and the nitrogen functionalities. The reaction methodology allows for the stereospecific formation of one C–C and one C–N bond across an alkene in a fully intermolecular sense, which is unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a novel cyclopentadienyl ligand to control the reactivity of Rh(III). The results provide a new route to functionalized alkenes and are expected to lead to the more convergent and stereoselective assembly of amine-containing acyclic molecules. 2015-10-21 2015-11-05 /pmc/articles/PMC4636455/ /pubmed/26503048 http://dx.doi.org/10.1038/nature15691 Text en http://www.nature.com/authors/editorial_policies/license.html#terms Users may view, print, copy, and download text and data-mine the content in such documents, for the purposes of academic research, subject always to the full Conditions of use:http://www.nature.com/authors/editorial_policies/license.html#terms
repository_type Open Access Journal
institution_category Foreign Institution
institution US National Center for Biotechnology Information
building NCBI PubMed
collection Online Access
language English
format Online
author Piou, Tiffany
Rovis, Tomislav
spellingShingle Piou, Tiffany
Rovis, Tomislav
Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group
author_facet Piou, Tiffany
Rovis, Tomislav
author_sort Piou, Tiffany
title Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group
title_short Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group
title_full Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group
title_fullStr Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group
title_full_unstemmed Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group
title_sort rh-catalyzed intermolecular syn-carboamination of alkenes via a transient directing group
description Alkenes are the most ubiquitous pro-chiral functional groups accessible to synthetic chemists. For this reason, difunctionalization reactions of alkenes are particularly important, as they can be used to access highly complex molecular architectures.1,2 Stereoselective oxidation reactions, including dihydroxylation, aminohydroxylation and halogenation reactions,3,4,5,6 are well-established methods for functionalizing alkenes. However, the intermolecular incorporation of both carbon- and nitrogen-based functionalities stereoselectively across an alkene has not been reported. In this manuscript, we describe the Rh(III)-catalyzed syn carboamination of alkenes initiated by a C–H activation event that uses enoxyphthalimides as the source of the carbon and the nitrogen functionalities. The reaction methodology allows for the stereospecific formation of one C–C and one C–N bond across an alkene in a fully intermolecular sense, which is unprecedented. The reaction design involves the in situ generation of a bidentate directing group and the use of a novel cyclopentadienyl ligand to control the reactivity of Rh(III). The results provide a new route to functionalized alkenes and are expected to lead to the more convergent and stereoselective assembly of amine-containing acyclic molecules.
publishDate 2015
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4636455/
_version_ 1613498647174971392

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