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DOI: 10.1055/s-0037-1611790
Hydroaminoalkylation of Allenes
Funding Information: Deutsche Forschungsgemeinschaft, (Grant/ Award Number: 'DO 601/9-1')Publication History
Received: 27 November 2018
Accepted after revision: 24 March 2019
Publication Date:
10 April 2019 (online)
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Abstract
The first examples of early-transition-metal-catalyzed hydroaminoalkylation reactions of allenes are reported. Initial studies performed with secondary aminoallenes led to the identification of a suitable titanium catalyst and revealed that under the reaction conditions, the initially formed hydroaminoalkylation products undergo an unexpected titanium-catalyzed rearrangement to form the thermodynamically more stable allylamines. The assumption that this rearrangement involves a reactive allylic cation intermediate provides a simple explanation of the fact that no successful early-transition-metal-catalyzed hydroaminoalkylations of allenes have previously been reported. As a result of the generation of the corresponding cation, the titanium-catalyzed intermolecular hydroaminoalkylation of propa-1,2-diene unexpectedly gives an aminocyclopentane product formed by incorporation of two equivalents of propa-1,2-diene.
Key words
allenes - amines - C–H activation - homogeneous catalysis - titanium - hydroaminoalkylationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0037-1611790.
- Supporting Information
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References and Notes
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For selected reviews on the hydroaminoalkylation of alkenes, see:
For group-3-metal-catalyzed hydroaminoalkylation reactions of alkenes with tertiary amines, see:
For selected examples of late-transition-metal-catalyzed hydroaminoalkylation reactions of alkenes, see:
For selected examples of group 4 metal catalysts for hydroaminoalkylation reactions, see:
For selected examples of group 5 metal catalysts for hydroaminoalkylation reactions, see:
For examples of titanium-catalyzed intramolecular hydroaminoalkylation reactions of aminoalkenes, see:
For selected examples of titanium-catalyzed allene hydroamination with primary amines, see:
For selected examples of hydroamination reactions with secondary amines achieved with neutral group 4 metal catalysts, see: