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1.2.2.1.2 Kumada–Tamao–Corriu Coupling Catalyzed by Well-Defined Palladium–N-Heterocyclic Carbene Species

DOI: 10.1055/sos-SD-223-00051

Ogasawara, M.Science of Synthesis: N-Heterocyclic Carbenes in Catalytic Organic Synthesis, (20161143.

Several well-defined palladium–NHC species 69 have been developed that are active for aryl–aryl Kumada–Tamao–Corriu coupling (Scheme 3).[‌9‌‌12‌] Mechanistic studies have revealed that the catalytically active palladium species are mono-NHC compounds.[‌13‌‌15‌] In accordance with this, the well-defined precatalysts possess the common structural motif that is a mono-NHC–palladium core with a ligand of easy dissociation. Precatalysts 68 have the bulky 2,6-diisopropylphenyl substituent on the nitrogens of the NHC moieties (IPr ligand in 6 and 7, SIPr in 8) and the corresponding N-mesityl counterparts are less effective.[‌9‌‌11‌] On the other hand, the N-mesityl NHC (SIMes) derivative is the optimal species in precatalyst 9.[‌12‌] Precatalysts 69 are all capable of coupling aryl chlorides under relatively mild conditions. Various hetaryl halides are equally reactive with these precatalysts. Additionally, the synthesis of tri- and tetra-ortho-substituted biaryls 12 is achieved using precatalyst 8.[‌11‌] The Kumada–Tamao–Corriu coupling of an alkenyl Grignard reagent has been reported with limited scope.[‌16‌]

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Meeeeeeeeee 8

Me8 M Me8 Meeeeeee (eee%) Meeeeeeeee Meeee (%) Mee
8-MM8M8 Me Me 8 (8) eeeeeee, 88 °M, 8 e 88 [‌8‌]
8-Mee Me Me 8 (8) eeeeeee, 88 °M, 8 e 88 [‌8‌]
Me Mee 8 (8) MMM, ee 88 [‌88‌]
8-M8MM8M8 Me Mee 8 (8) MMM, 88 °M >88 [‌88‌]
Me 8-eeeeeeee 8 (8) MMM, ee >88 [‌88‌]
8,8-Me8M8M8 Me 8,8-Me8M8M8 8 (8.88) MMM, 88 °M, 88 e 88 [‌88‌]
8-eeeeeee Me 8-Mee 8 (8.8) MMM, 88 °M, 88 e >88 [‌88‌]
8-eeeeeee Me 8-MeMM8M8 8 (8.8) MMM, 88 °M, 8 e 88 [‌88‌]
8-eeeeeeee Me 8-eeeeeeee 8 (8) MeMe, MMM, ee, 88 e 88 [‌88‌]
8-eeeeeee Me 8-Mee 8 (8) MeMe, MMM, ee, 88 e 88 [‌88‌]

Me 8888, Meeeeee eee ee-eeeeeee eeeeeeee eee “eeeeeeeeee” Meeeee–Meeee–Meeeee eeeeeeee ee ee- ee eeeeeeeeeeeeeeee eeee 8 eeeeeeeeee ee ee eeee Meeeeeee eeeeeeeeeee (Meeee 8).[‌88‌] Me eee eeeeeeee ee MMMMMM-MMeee eeeeeeeeeee 88, eeeee eeeee e eeee eeeee MMM eeeeee, ee eeeeeeeee eeeeeee ee 8,8-eeeeeeeeeeeeeee eee eeeeeeeeeeeeeee eeeeeee eeeee eee eeeeee eeeeeeeeeee eeeeeee (e-eeeeeeeee) eeeeeeeeeeeee (88% eeeeeeeeeee) eee eee eeeeeeeee ee eee eeeeeeeeeeeeeee eeeeeee (8-eeeeeeeeeeeeee) ee eeeeeee. Mee eeeeeeeeeeee eeeeee eeeee eeeeeeeee eee eeeee eeeeeee eeeee eee eeeeeeeee eeeeeeeeee, eee eeeeeee eeeeeeeeeeeee eeeeeeeeee eeee eee eeeeeeeeeeeee eeeeeeeeeee eeeeeeee ee eeee ee eeeeeeeee eeeeeeeeeee, eeee eeee ee eeeeeeeee eeeeeeee ee eee eeee eeeeeeeeeee. Mee eeeeeeeeee eeeee eeeeeeee ee eee eeeeeee ee eeeeeeeeeeeee eeeeeeeeee; eee Meeeee–Meeee–Meeeee eeeeeeee ee eee- ee eeeeeeeeeeeeeeeeee eeee eeeeeeeee eeeeeee ee eeeeeeeeeeeeeee eeeeeee eeeeeeeee ee 88 eeeeeeee eee eeeeeeeeeeeee eeeeeeeeeeeee eeeeeeee eeee eeee eeee eeeeeeeeeee. Mee eeeeeeeeeeee eeeeeeeeee eeeee eeeeeeee ee eeeeeeeeeeeeeee eee eeeeeeee ee 8888 ee eee eeee eeeeeeee eeeee eee eee Meeeeee eeeeeeee eeee eeeeeeeeee eeeeeeee eeeeeeeee ee MMMMMM-MMe eeeeeee 8.[‌88‌]

Meeee 8 Meeeeeeeee Meeee Meeeeeee ee Meeeeeeeeeeeee eeee ee Meeeeeeee Meeeee ee Meeeeeeeeeeee Meeeeee[‌88‌]

Meeeeeee Meeeeeeee Meeee Meeeeee Meeeeee Meeeee Meeee (%) Mee
Meeeeeeeeeeee Meeeeeee Meeeeee
8:88 88 [‌88‌]
8:88 88 [‌88‌]
<8:>88 88 [‌88‌]
8:88 88 [‌88‌]
8:88 88 [‌88‌]

e Meeee (eeeeeeeeeeeee/eeeeeeeeeee).

MMM–eeeeeeeee(8) eeeeeeeeeeeeee eeeeeee 88 ee eeeeeeeee eee eee Meeeee–Meeee–Meeeee eeeeeeee eeeeeee eeeee eeeeeeeee eee eeeeeeeeeeeee eeeeeeee (Meeeee 8).[‌88‌] Mee ee eee eeee eeeeeeee eeeeeeeeee eee eeee eeeeeeee eeeee eee eee Meeeee–Meeee–Meeeee eeeeeeee, eeeeeeeeeeeeeee eeee eee eeeee eeeeeeeeeeee eeee Meeeeeee eeeeeeee eee eeeeeeeee ee eeee eeeeee, eee eeeeeee eee eeeee eeeeee eee eee eeeeeeee ee e eeeeeeeeeee eeeeee. Meeee eeeeeeee ee eee eeeeeeeeeeeee eeeeeeeeee eee eeeeeee ee eeeeeee eeeee eeeeee; eeeeeeeee eeeee eeeeeeeee eeeeee ee eeeeeee ee eeeeeeeeeeeee eeeeee eeeeee.

Meeeee 8 Meeee–Meee Meeeee–Meeee–Meeeee Meeeeeee Meeeeeeee ee e Meee-Meeeeee Meeeeeeee–MMM Meeeeee[‌88‌]

Meeeeeeeeee 8

M8 Me8 Meeee (%) Mee
(MM8)8Me Me 88 [‌88‌]
(MM8)8Me 8-Mee 88 [‌88‌]
eMe 8-Mee 88 [‌88‌]
(MM8)8MM8Me 8-Mee 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeee 88; Meeeeee Meeeeeeee eee Meeeee–Meeee–Meeeee Meeeeeee ee Meee Meeeeee eee Meeeeeeeeeeee Meeeeeee:[‌88‌]

Meeee eee, e eeee eeeeeeee eeee e eeeeeee eee eee eeeeeee eeee MMMMMM-MMe eeeeeee 8 (8.8 ee, 8.88 eeee, 8 eee%), eeeeee eeee e eeeeee, eee eeeeee eeee eeeee. Meeeeeeeeee eeeeeeee eeee eeeee ee eeeeeee eee eee eeeeeee eee eeeeeee eee 8–8 eee, eeeee eeeee eee eeee eeeeee 88 (8.8 eeee), eee eeeeeeee (MM/MM eeeeeeee eeeeeeee; 88 µM) eeee eeeeeeee eee eeeeeee. Meeeeeeeeeeee, ee eee eeee eeeeee 88 eee eeeee ee ee, ee eee eeeeeee eee eee eeeee ee eee eeee eeeee eee eeeeeeeee eeeeeeee ee eee eeeee eeeeeee. Meeee 8–8 eee ee eeeeeeee, eee Meeeeeee eeeeeee 88 (8.88 ee 8.8 eeee, 8.8 ee 8.8 eeeee) eee eeeee ee eee eeeee eeee ee eeeeeee. Mee eeeeee eee eeeeeeee eeee e Meeeee-eeeee eeeee eee eeeee ee eeeee eeeeeeeeee eee eee eeeeeee eee eeeeeee ee eeee eee eeeeeeeeeeeee 88 e ee ee/88 °M eeeee ee MM/MM eee/ee MMM eeeeeeee. Meee eeeeeeeee eeee eeeeee eeeeeeee, 8 M Me8(eeee) eeee [eeeeeeee eeee eeee eee MeMM (8 eeeee)] eee eeeee, eee eee eeee eee eeeeeee eee 8 eee, eee eeee eeeeeeeeeee ee e eeeeeeeeee eeeeee. Mee eeeeee eeee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeee eeeeeeeeeeee eeeeee eeee eeeeeeeee M8M eee eeeee. Meeee eeeeee (MeMM8), eee eeee eee eeeeeeee eee eeeeeeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee).

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