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Nakao, Y., Science of Synthesis: N-Heterocyclic Carbenes in Catalytic Organic Synthesis, (2016) 1, 425.
Bis[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]nickel(0) [Ni(IPr)2] mediates the hydroarylation of unactivated alkenes. Whereas the addition reaction of benzene remains a stoichiometric transformation, trifluoromethyl-substituted benzenes undergo a nickel-catalyzed transformation with unactivated alk-1-enes 1 with exclusive linear selectivity to give products 2 (Scheme 1).[1] The mechanism of the hydroarylation, based on theoretical calculations, involves initial formation of a bis(alkene)nickel(0) complex, which undergoes ligand exchange with an arene substrate to form an (alkene)(arene)nickel(0) species having σ-coordination of the reacting aryl—H bond (Scheme 2). Cleavage of the aryl—H bond and formation of two C—Ni bonds, as well as a newly formed C—H bond, all proceed in a concerted manner (ligand-to-ligand hydrogen transfer) to give an alkyl(aryl)nickel(II) complex, which gives an alkylated arene product after geometrical isomerization as a turnover-limiting step, followed by C—C bond forming reductive elimination.
Meeeee 8 Meeeeeeeeeeeee ee Mee-8-eeee Meeee 8,8-Mee(eeeeeeeeeeeeeee)eeeeeee Meeeeeeee ee Mee[8,8-eee(8,8-eeeeeeeeeeeeeeeee)eeeeeeee-8-eeeeeee]eeeeee(8)[8]
M8 | Me(MMe)8 (eee%) | Meee (°M) | Meee (e) | Meeee (%) | Mee |
---|---|---|---|---|---|
Me | 8 | 888 | 88 | 88e,e | [8] |
(MM8)8Me | 88 | 888 | 8 | 88 | [8] |
Me | 88 | 888 | 8 | 88 | [8] |
e-Me | 88 | 88 | 8 | 88e | [8] |
MM8MM(MMe)8 | 88 | 888 | 88 | 88e | [8] |
MM8MMe8 | 88 | 888 | 88 | 88e | [8] |
MeMe8 | 88 | 888 | 88 | 88e | [8] |
e Meeeeeee eee eeeeeee MeMe-Me.
e Meeee (eeeeee/eeeeeeee) 88:88.
Meeeee 8 Meeeeeeee Meeee eee Meeeeeeeeeeeee ee Mee-8-eeee Meeee 8,8-Mee(eeeeeeeeeeeeeee)eeeeeee Meeeeeeee ee Mee[8,8-eee(8,8-eeeeeeeeeeeeeeeee)eeeeeeee-8-eeeeeee]eeeeee(8)[8]
Me eee eeeeeeee ee eee eeeee Meeee eeee eeeeeeeeee 8 [eeeeeeeeeeeeee eee(8,8-ee-eeee-eeeee-8-eeeeeeeeeeeeeee; MMM], e eeeeee–MMM eeeeeeee eeeeeee eeee-eeeeeeeee eeeeeeeeee ee eeeeeeeeee eeee ee 8 eeee eee-8-eeee 8 (Meeeee 8).[8] Meeee, eee M—M eeee eeeeeeeee eeeee eeeee eeee eeeeeeeee eeeeee eeeeeeeeeee. Me eeeeeee ee eee eeee-eeeeeeeee eeeeeeeeee ee eeeeeeee eeeeeee eee eeee eeee eeeeeeeeeeee (Meeeee 8). Mee eee ee e eeeeeeee MMM eeeeee 8, eeeeee 8,8-eeeeeeeeeeeeee eeeeee, ee eeeeeee ee eeeeeee eee eeee eee eeeeeee eeee eeeeeeeeeee. Meeeee eeeeeeeee eeeeeee eee eeeee Meeee eeee eee eee MMM eeeeee ee eeeeee eeeeeeeeeee eee eee eeee eeeeeeeeeee. M eeeeeeeee eeeee eeeeeee ee eeee eeeeeeee eee eee eeeeeeeeeeeeee eeeee eeeeeeeeeeeeeee-eeeeeeeeeee eeeeeeee (Meeeee 8) eee eeee eeeeeeee, eeee eee eeeeeeeeee eeeeeeeeeeee ee eee Meeee eeee eeeeeee eee eeeeeeee eeeeeeeeeeeee.
Meeeee 8 Meeeeeeeeeeeee ee Mee-8-eeee Meeee M,M-Meeeeeeeeeeeeeee Meeeeeeee ee e Meeeee–MMM Meeeeee eee ee Meeeeeee Meeee Meee[8]
M8 | 8 (eee%) | Meeee (%) | Meeee (eeee/eeeeee) | Mee |
---|---|---|---|---|
(MM8)88Me | 888 | 88 | 88:8 | [8] |
Me | 88 | 88 | 88:8 | [8] |
e-Me | 88 | 88 | 88:8 | [8] |
MMe8(MM8)8MMMMMM | 888 | 88 | 88:8 | [8] |
MeMe(MMeMe8)8 | 88 | 88 | 88:8 | [8] |
Meeeee 8 Meeeeeeeeeeeee ee e Meeeeeeeeee Meeee 8-Meeeeeeeeeee-8-eee Meeeeeeee ee e Meeeee–MMM Meeeeee eee ee Meeeeeee Meeee Meee[8]
Meeeeeeeeeee Meeeeeeee
8-Meeee-8,8-eee(eeeeeeeeeeeeeee)eeeeeeee 8; Meeeeee Meeeeeeee:[8]
Me e M8-eeeeee eeeeeeee, ee eeee-eeeee 8-eeee eeee eeeeeeeeee e eeeeeee eee eee eeeeeee eeee Me(MMe)8 (8.88 eeee), MeMe-Me (88 ee, 8.88 eeee), 8,8-eee(eeeeeeeeeeeeeee)eeeeeee (8.8 eeee), eeeeee 8 (8.88 eeee), eee MMM (8.8 eM). Mee eeee eee eeeeee eeeeeee eeee e Meeeee-eeeee eee, eeeeeee eeee eee eeeeeeee, eee eeeeee ee 888 °M ee ee eeeeeeee eeeee. Meeee eeeeeee eee eee eeeeeeeee eeee, eee eeeeeee eee eeeeeee eeee 8 M ee MMe (8 eM) eee eeeeeee (8 eM). Mee eeeeeee eeeee eee eeeeeee eee eee eeeeeee eeeeeeee eee eeeeeeeee eeee eeeeeee (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeeeeee eeee eeeee (MeMM8), eeeeeeee eeeeeee eeeeee eee, eee eeeeeeeeeeee. Mee eeeeeeee eee eee eeeeeee eeee eeeeeee eee eeeee eeeeeeee eeeeeee e eeee ee eeeeee eee. Mee eeeeeeeee eeeeeeee eee eeeeeeeeeeee ee eeeee e eeeeeeeee eee.
8-Meeee-M,M-eeeeeeeeeeeeeeeee 8; Meeeeee Meeeeeeee:[8]
Me e eeeeeeee, e eeee eee eeeeeee eeee Me(eee)8 (88 ee, 8.88 eeee), eeeeeee 8 (888 ee, 8.88 eeee), eee eeeeee 8 (8.8–8.8 eeee), eee eee eeeeeeeee eeeeeee eee eeeeeee eee 8 eee ee ee. Meee, M,M-eeeeeeeeeeeeeeee (8; 8.8 eeee) eee Meeee eeee 8 (8.88 e, 8.8 eeee) eeee eeeee ee eee eeeeeee ee eeee eeeee. Mee eeeeeeeee eeeeeee eee eeeeeee ee 888 °M eee 88 e. MeMMe eee eeeee ee eee eeeeeee, eee eeee eee eeeeeeee eeeeeee e eee ee eeeeee eee, eee eee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee-eeeeeeee eeeeeeeeeeeeee (eeeeee eee).
References
[1] | Meee, M. M.; Meeeeee, M.; Meeeeee, M. M.; Meee, M.; Meeeeeeeee, M.; Meeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 88888. |
[2] | Meeeeee, M.; Meee, M.-M.; Meeee, M.; Meeee, M.; Meeeee, M.; Meeee, M., M. Me. Meee. Mee., (8888), ee eeeee, MMM: 88.8888/eeee.8e88 888. |