2023
DOI: 10.1002/anie.202313848
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Phenoxythiazoline (FTz)‐Cobalt(II) Precatalysts Enable C(sp2)–C(sp3) Bond‐Formation for Key Intermediates in the Synthesis of Toll‐like Receptor 7/8 Antagonists**

L. Reginald Mills,
Francesca Di Mare,
David Gygi
et al.

Abstract: Evaluation of the relative rates of the cobalt‐catalyzed C(sp2)–C(sp3) Suzuki–Miyaura cross‐coupling between the neopentylglycol ester of 4‐fluorophenylboronic acid and N‐Boc‐4‐bromopiperidine established that decreasing the size of the N‐alkyl substituents on the phenoxyimine (FI) supporting ligand accelerated the overall rate of the reaction. This trend inspired the design of optimal cobalt catalysts with phenoxyoxazoline (FOx) and phenoxythiazoline (FTz) ligands. An air‐stable cobalt(II) precatalyst, (FTz)C… Show more

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Cited by 4 publications
(6 citation statements)
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“…The solution concentration of (FI)nickel(II)−aryl ( 20) is proportional to the rate of product formation (5) such that the alkyl radical capture is the turnover-limiting step for product formation. Radical capture yields (FI)nickel(III) intermediate 26, 63 which presumably undergoes C(sp 2 )−C(sp 3 ) bond-forming reductive elimination, 64 yielding cross-coupled product (5) and a putative (FI)nickel(I) intermediate (18) (20). It should be emphasized that product-forming propagation occurs in excess of ten times per rate-limiting initiation event, such that the rate of product formation is not proportional to a single turnoverlimiting step in the classical sense.…”
Section: Journal Of the American Chemical Societymentioning
confidence: 99%
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“…The solution concentration of (FI)nickel(II)−aryl ( 20) is proportional to the rate of product formation (5) such that the alkyl radical capture is the turnover-limiting step for product formation. Radical capture yields (FI)nickel(III) intermediate 26, 63 which presumably undergoes C(sp 2 )−C(sp 3 ) bond-forming reductive elimination, 64 yielding cross-coupled product (5) and a putative (FI)nickel(I) intermediate (18) (20). It should be emphasized that product-forming propagation occurs in excess of ten times per rate-limiting initiation event, such that the rate of product formation is not proportional to a single turnoverlimiting step in the classical sense.…”
Section: Journal Of the American Chemical Societymentioning
confidence: 99%
“…From the potassium isopropoxide (FI)nickel(II)−aryl complex (21), β-hydride elimination and C−H reductive elimination releases arene (24) and generates potassium (FI)nickel(0)ate−acetone complex (13). Potassium (FI)nickel(0)ate ( 13) readily activates alkyl bromide (4), forming an alkyl radical (25) and a putative (FI)nickel(I) intermediate (18), completing radical (re)initiation.…”
Section: ■ Introductionmentioning
confidence: 99%
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