Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2017 May 31;139(21):7180-7183.
doi: 10.1021/jacs.7b03480. Epub 2017 May 19.

Enantioselective Intermolecular Addition of Aliphatic Amines to Acyclic Dienes with a Pd-PHOX Catalyst

Nathan J Adamson  1 , Ethan Hull  1 , Steven J Malcolmson  1
Affiliations

Enantioselective Intermolecular Addition of Aliphatic Amines to Acyclic Dienes with a Pd-PHOX Catalyst

Nathan J Adamson et al. J Am Chem Soc. .

Abstract

We report a method for the catalytic, enantioselective intermolecular addition of aliphatic amines to acyclic 1,3-dienes. In most cases, reactions proceed efficiently at or below room temperature in the presence of 5 mol % of a Pd catalyst bearing a PHOX ligand, generating allylic amines in up to 97:3 er. The presence of an electron-deficient phosphine within the ligand not only leads to a more active catalyst but also is critical for achieving high site selectivity in the transformation.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1
Catalytic Enantioselective Intermolecular Diene Hydroamination Reactions
Scheme 2
Scheme 2
Initial Mechanistic Investigations of Pd–PHOX-Catalyzed Diene Hydroaminations
See this image and copyright information in PMC

References

    1. For reviews, see: Reznichenko AL, Nawara-Hultzsch AJ, Hultzsch KC. Top. Curr. Chem. 2013;343:191.Huang L, Arndt M, Gooßen K, Heydt H, Gooßen LJ. Chem. Rev. 2015;115:2596.Coman SM, Parvulescu VI. Org. Process Res. Dev. 2015;19:1327.

    1. For reviews on Cu-catalyzed umpolung approaches to hydroamination of unsaturated hydrocarbons, see: Hirano K, Miura M. Pure Appl. Chem. 2014;86:291.Pirnot MT, Wang Y-M, Buchwald SL. Angew. Chem. Int. Ed. 2016;55:48.

    1. Löber O, Kawatsura M, Hartwig JF. J. Am. Chem. Soc. 2001;123:4366. - PubMed

    1. For enantioselective Pd-catalyzed aniline additions to styrenes, see: Kawatsura M, Hartwig JF. J. Am. Chem. Soc. 2000;122:9546.Hu A, Ogasawara M, Sakamoto T, Okada A, Nakajima K, Takahashi T, Lin W. Adv. Synth. Catal. 2006;348:2051.

    1. For mechanistic studies of Pd-catalyzed styrene and diene hydroamination with anilines, see: Nettekoven U, Hartwig JF. J. Am. Chem. Soc. 2002;124:1166.Johns AM, Utsunomiya M, Incarvito CD, Hartwig JF. J. Am. Chem. Soc. 2006;128:1828. For a study with a Ni catalyst and alkyl amines, see: Pawlas J, Nakao Y, Kawatsura M, Hartwig JF. J. Am. Chem. Soc. 2002;124:3669.

Publication types

LinkOut - more resources