Journal
ACS CATALYSIS
Volume 8, Issue 6, Pages 5328-5339Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.8b01005
Keywords
nickel; C-N cross-coupling; amination; ligand design; density functional theory
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Funding
- Natural Sciences and Engineering Research Council of Canada [RGPIN-2014-4807, RGPIN-2017-04297, RGPIN-2016-05795]
- Natural Sciences and Engineering Research Council of Canada
- Killam Trusts
- Dalhousie University
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We report herein on the synthesis and catalytic application of a family of o-phenylene-bridged bisphosphine ancillary ligands featuring a bulky N-heterocyclic phosphine (NHP) donor fragment paired with an adjacent PR2 donor group (R = alkyl, aryl), whereby the incorporation of phosphorus into either a saturated or unsaturated heterocyclic ring serves as a means of modulating the donicity of the NHP fragment. Screening of these ancillary ligands in representative nickel-catalyzed C(sp(2)) N cross-coupling test reactions allowed for the identification of one variant, featuring a saturated NHP structure and an adjacent diphenylphosphino donor group (i.e., NHP-DalPhos), as being particularly effective in reactions involving primary alkylamines. Notably, application of the derived precatalyst (NHP-DalPhos)NiCl(o-tolyl) (C1) enabled the typically challenging monoarylation of structurally diverse primary alkylamines with (hetero)aryl chlorides or bromides at room temperature. Also described are the results of our comparative density functional theory computational analysis of nickel-catalyzed primary alkylamine C(sp(2)) N cross-couplings employing PAd-DalPhos or NHP-DalPhos.
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