Cobalt-Catalyzed C(sp 2 )-C(sp 3 ) Suzuki-Miyaura Cross-Coupling Enabled by Well-Defined Precatalysts with L,X-Type Ligands.
| Autor: | Mills LR; Department of Chemistry, Princeton University, Princeton, NJ 08544, USA., Gygi D; Chemical Process Development, Bristol Myers Squibb Company, New Brunswick, New Jersey 08903, USA., Ludwig JR; Department of Chemistry, Princeton University, Princeton, NJ 08544, USA., Simmons EM; Chemical Process Development, Bristol Myers Squibb Company, New Brunswick, New Jersey 08903, USA., Wisniewski SR; Chemical Process Development, Bristol Myers Squibb Company, New Brunswick, New Jersey 08903, USA., Kim J; Department of Chemistry, Princeton University, Princeton, NJ 08544, USA., Chirik PJ; Department of Chemistry, Princeton University, Princeton, NJ 08544, USA. |
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| Jazyk: | angličtina |
| Zdroj: | ACS catalysis [ACS Catal] 2022 Feb 04; Vol. 12 (3), pp. 1905-1918. Date of Electronic Publication: 2022 Jan 20. |
| DOI: | 10.1021/acscatal.1c05586 |
| Abstrakt: | Cobalt(II) halides in combination with phenoxy-imine (FI) ligands generated efficient precatalysts in situ for the C(sp 2 )-C(sp 3 ) Suzuki-Miyaura cross coupling between alkyl bromides and neopentylglycol (hetero)arylboronic esters. The protocol enabled efficient C-C bond formation with a host of nucleophiles and electrophiles (36 examples, 34-95%) with precatalyst loadings of 5 mol%. Studies with alkyl halide electrophiles that function as radical clocks support the intermediacy of alkyl radicals during the course of the catalytic reaction. The improved performance of the FI-cobalt catalyst was correlated with decreased lifetimes of cage-escaped radicals as compared to diamine-type ligands. Studies of the phenoxy(imine)-cobalt coordination chemistry validate the L,X interaction leading to the discovery of an optimal, well defined, air-stable mono-FI cobalt(II) precatalyst structure. |
| Databáze: | MEDLINE |
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