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Synlett 2017; 28(16): 2057-2065
DOI: 10.1055/s-0036-1589077
DOI: 10.1055/s-0036-1589077
synpacts
Regioselective Hydroamination Using a Directed Nucleopalladation/Protodepalladation Strategy
We gratefully acknowledge TSRI and Pfizer, Inc. for financial support, as well as the Donald E. and Delia B. Baxter Foundation and the National Science Foundation (NSF/DGE-1346837) for predoctoral fellowships (J.A.G.)Further Information
Publication History
Received: 15 May 2017
Accepted after revision: 21 June 2017
Publication Date:
02 August 2017 (online)
Abstract
Alkene hydroamination is an attractive approach for converting alkenes into structurally complex amine products. Several different strategies have been pursued over the past few decades to achieve this historically challenging reaction. One of the key issues associated with this transformation is control of regioselectivity, which is particularly difficult for internal non-conjugated alkenes. Our group has recently found success using a removable bidentate auxiliary to control regioselectivity and stabilize the key nucleopalladated intermediate in a palladium(II)-catalyzed alkene hydroamination with N–H nucleophiles. This article describes the historical context for this work, the underlying conceptual logic, our results to date, and the future outlook.
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For reviews on alkene hydroamination, see:
For selected examples of alkene hydroamination reactions catalyzed by CuH species, see:
For related examples with Pd, see:
For selected examples of hydrogen atom transfer (HAT) alkene hydroamination reactions, see:
For selected examples of intermolecular alkene hydroamination reactions involving aminometalation using metals other than palladium, see:
Several examples of intermolecular hydroamination of conjugated alkenes catalyzed by palladium–phosphine complexes have been described. A commonly invoked mechanistic paradigm for these transformations involves oxidative addition of Pd(0) to HX, followed by hydropalladation to generate a π-allyl (or analogous) intermediate, and finally attack of the nitrogen nucleophile:
For selected examples of photoredox alkene hydroamination reactions, see:
For selected examples of Cope type hydroamination reactions, see:
For reviews on nucleopalladation, see:
For selected examples of catalytic reactions involving nucleopalladation, see:
For reviews on Wacker oxidation, see:
For reviews on aza-Wacker reactions, see:
For pioneering reports on intermolecular aza-Wacker reactions, see: