(Phenoxyimine)nickel-Catalyzed C(sp2)-C(sp3) Suzuki-Miyaura Cross-Coupling: Evidence for a Recovering Radical Chain Mechanism

被引:3
作者
Mills, L. Reginald [1 ]
Simmons, Eric M. [2 ]
Lee, Heejun [2 ]
Nester, Eva [1 ]
Kim, Junho [1 ]
Wisniewski, Steven R. [2 ]
Pecoraro, Matthew V. [1 ]
Chirik, Paul J. [1 ]
机构
[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA
[2] Bristol Myers Squibb Co, Chem Proc Dev, New Brunswick, NJ 08903 USA
基金
加拿大自然科学与工程研究理事会;
关键词
ALKYL ELECTROPHILES; ETHYLENE POLYMERIZATION; REDUCTIVE ELIMINATION; OXIDATIVE ADDITION; NICKEL; COMPLEXES; HALIDES; REACTIVITY; CATALYSTS; TRANSMETALATION;
D O I
10.1021/jacs.4c01474
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Phenoxyimine (FI)-nickel(II)(2-tolyl)(DMAP) compounds were synthesized and evaluated as precatalysts for the C(sp(2))-C(sp(3)) Suzuki-Miyaura cross coupling of (hetero)arylboronic acids with alkyl bromides. With 5 mol % of the optimal ((MeFI)-F-OMe)Ni(Aryl)(DMAP) precatalyst, the scope of the cross-coupling reaction was established and included a variety of (hetero)arylboronic acids and alkyl bromides (>50 examples, 33-97% yield). A beta-hydride elimination-reductive elimination sequence from reaction with potassium isopropoxide base, yielding a potassium (FI)nickel(0)ate, was identified as a catalyst activation pathway that is responsible for halogen atom abstraction from the alkyl bromide. A combination of NMR and EPR spectroscopies identified (FI)nickel(II)-aryl complexes as the resting state during catalysis with no evidence for long-lived organic radical or odd-electron nickel intermediates. These data establish that the radical chain is short-lived and undergoes facile termination and also support a "recovering radical chain" process whereby the (FI)nickel(II)-aryl compound continually (re)initiates the radical chain. Kinetic studies established that the rate of C(sp(2))-C(sp(3)) product formation was proportional to the concentration of the (FI)nickel(II)-aryl resting state that captures the alkyl radical for chain propagation. The proposed mechanism involves two key and concurrently operating catalytic cycles; the first involving a nickel(I/II/III) radical propagation cycle consisting of radical capture at (FI)nickel(II)-aryl, C(sp(2))-C(sp(3)) reductive elimination, bromine atom abstraction from C(sp(3))-Br, and transmetalation; and the second involving an off-cycle catalyst recovery process by slow (FI)nickel(II)-aryl -> (FI)nickel(0)ate conversion for nickel(I) regeneration.
引用
收藏
页码:10124 / 10141
页数:18
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