You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via3.12.1.1.1 Reaction of Electron-Poor Alkenes
Please login to access the full content or check if you have access via
Shibasaki, M.; Ohshima, T.; Itano, W., Science of Synthesis: Stereoselective Synthesis, (2011) 3, 485.
Electron-poor alkenes, typically acrylates and styrene derivatives, generally lead to the exclusive formation of the E-β-substituted product 17, 22, and 25 (Tables 1–3). Substrates that are reactive in the oxidative addition, e.g. aryl iodides and activated aryl bromides, react smoothly under the classical Mizoroki–Heck conditions provided that the palladium complex has at least three labile or hemilabile ligands, which typically implies a phosphine-free palladium complex. In fact, classical systems are the most robust and often provide very high turnover numbers. Strongly coordinating ligands, such as phosphines, often retard the reaction. Unactivated aryl bromides and activated aryl chlorides generally require high reaction temperatures (>140 °C), higher catalyst loadings (0.05–0.5 mol%), and polar solvents to provide high yields. Palladacycles,[20,21] heterocyclic carbene complexes,[22] and solid-supported palladium complexes[23] are also effective for these substrates. Electron-rich and bulky ligands, such as tri-tert-butylphosphine, form highly active and coordinatively unsaturated palladium complexes, making unreactive aryl chlorides suitable substrates for this reaction.[24,25] The Mizoroki–Heck reaction of aryl trifluoromethanesulfonates proceeds under mild conditions through a “cationic pathway” (see Section 3.12.1.1.2), where bidentate diphosphines are usually employed as the ligand.
Meeee 8 Meeeeeee–Meee Meeeeeee ee Meee Meeeeee eeee Meeeeeee-Meee Meeeeee[88,88–88]
M8 | M8 | MMM | Meeeeeeeee | Meeee (%) | Mee |
---|---|---|---|---|---|
8-M8MM8M8 | M | MM8Me | MeMe8(MMe8)8 (8 eee%), Me8M (8 eeeee), MeMM, 88 °M, 88 e | 88 | [88] |
Me | M | MM8Me | Me(MMe)8 (8 eee%), Me8M (8 eeeee), 888 °M, 8 e | 88 | [88] |
Me | M | MM8Me | 88 (8.8 eee), Me8M (8.8 eeeee), MMM, 888 °M, 88 e | 888 | [88] |
Me | M | MM8Me | Me(eee)8 (8.888 eee%), 88 (8.888 eee%), Me8M (8.8 eeeee), MMM, 888 °M, 88 e | >88 | [88] |
Me | M | MM8Me | Me/M (8.888 eeee), Me8M (8.8 eeeee), eeeee eeeeee 88, 888 °M, 88 e | 88 | [88] |
Me | M | MM8e-Me | 88 (8.8 eee%), Me8MM8 (8.8 eeeee), MMM, eeeee eee, 888 °M, 8–8 e | 88 | [88] |
Me | M | MM | Me(MMe)8 (8 eee%), MMMM (88 eee%), MeMMM8 (8 eeeee), M8M, 88–88 °M, 88 e | 88 | [88] |
Me | M | Me | 88 (8 eee%), MeMMe (8.8 eeeee), MMM, eeeee eee, eeeeee, 8 e | 88 | [88] |
Me | M | 8-M8MM8M8 | Me(MMe)8 (8 eee%), Me8M (8 eeeee), 888 °M, 8 e | 88 | [88] |
8-Mee | M | MM8M | Me(MMe)8 (8 eee%), Meeeeeeee MMM-888 eeeee (888 e · eee−8), MMM, 88 °M, 8 e | 88 | [88] |
8-Mee | Me | MM8M | Me(MMe)8 (8 eee%), Meeeeeeee MMM-888 eeeee (888 e · eee−8), MMM, 88 °M, 8 e | 88 | [88] |
8-Mee | Me | MM8Me | Me(MMe)8 (8 eee%), Meeeeeeee MMM-888 eeeee (888 e · eee−8), MMM, 88 °M, 8 e | 88 | [88] |
8-Mee | Me | MM8eMe | Me(MMe)8 (8 eee%), Meeeeeeee MMM-888 eeeee (888 e · eee−8), MMM, 88 °M, 8 e | 88 | [88] |
8-Mee | M | Me | Me(MMe)8 (8 eee%), Meeeeeeee MMM-888 eeeee (888 e · eee−8), MMM, 88 °M, 8 e | 88 | [88] |
8-MeMM8M8 | M | Me | Me(MMe)8 (8 eee%), Meeeeeeee MMM-888 eeeee (888 e · eee−8), MMM, 88 °M, 8 e | 88 | [88] |
Meeee 8 Meeeeeee–Meee Meeeeeee ee Meee Meeeeeee eeee Meeeeeee-Meee Meeeeee[88,88,88,88–88]
M8 | M8 | MMM | Meeeeeeeee | Meeee (%) | Mee |
---|---|---|---|---|---|
8-M8MM8M8 | M | MM8Me | Me(MMe)8 (8.888 eee%), (8-Mee)8M (8.888 eee%), MeMMe (8.8 eeeee), MMM, 888 °M, 8 e | 88 | [88] |
8-M8MM8M8 | M | MM8Me | [Me(η8-M8M8)Me]8/88 (8:8; 88 eee), M8MM8 (8 eeeee), MMM, 888 °M, 88 e | 888 | [88] |
8,8-(M8M)8M8M8 | M | MM8Me | [Me(η8-M8M8)Me]8/88 (8:8; 8.88 eee), M8MM8 (8 eeeee), MMM, 888 °M, 88 e | 888 | [88] |
8-MeM8M8 | M | MM8Me | [Me(η8-M8M8)Me]8/88 (8:8; 8 eee), M8MM8 (8 eeeee), MMM, 888 °M, 88 e | 88 | [88] |
8-MMMM8M8 | M | MM8Me | 88 (8 eee), MeMMe (8.8 eeeee), MMM, 888 °M, 88 e | >88 | [88] |
8-eeeeeeee | M | MM8Me | [Me(η8-M8M8)Me]8/88 (8:8; 888 eee), M8MM8 (8 eeeee), MMM, 888 °M, 88 e | 88 | [88] |
8-eeeeeee | M | MM8Me | [Me(η8-M8M8)Me]8/88 (8:8; 88 eee), M8MM8 (8 eeeee), MMM, 888 °M, 88 e | 88 | [88] |
Me | M | MM8Me | 88 (8 eee), Me8MM8 (8.8 eeeee), MMM, 888 °M, 88 e | 88 | [88] |
Me | M | MM8Me | 88 (8.8 eee%), Me8MM8, MMM, 888 °M, 88 e | 888 | [88] |
Me | M | MM8Me | Me(eee)8 (8.8 eee%), 88 (8.8 eee%), Me8M (8.8 eeeee), MMM, ee, 88 e | 88 | [88] |
Me | M | MM8Me | [Me(η8-M8M8)Me]8/88 (8:8; 888 eee), M8MM8 (8 eeeee), MMM, 888 °M, 88 e | 88 | [88] |
8-MeMM8M8 | M | MM8Me | [Me(η8-M8M8)Me]8/88 (8:8; 888 eee), M8MM8 (8 eeeee), MMM, 888 °M, 88 e | 88 | [88] |
Me | M | Me | 88 (8 eee%), MeMMe (8.8 eeeee), MMM, eeeee eee, eeeeee, 8 e | >88 | [88] |
Me | M | Me | Me(MMe)8 (8 eee%), Me8M (8 eeeee), MMM (MM 8888), 88 °M, 88 e | 88 | [88] |
Me | M | Me | [Me(η8-M8M8)Me]8/88 (8:8; 88 eee), M8MM8 (8 eeeee), MMM, 888 °M, 88 e | 88 | [88] |
8-MeMM8M8 | M | Me | Me(MMe)8 (8 eee%), Me8M (8 eeeee), MMM (MM 8888), 88 °M, 88 e | 88 | [88] |
8-MeMM8M8 | M | Me | [Me(η8-M8M8)Me]8/88 (8:8; 88 eee), M8MM8 (8 eeeee), MMM, 888 °M, 88 e | 88 | [88] |
Meeee 8 Meeeeeee–Meee Meeeeeee ee Meee Meeeeeeee eeee Meeeeeee-Meee Meeeeee[88,88,88–88]
M8 | M8 | M8 | MMM | Meeeeeeeee | Meeeeee Meeee | Meeee (%) | Mee |
---|---|---|---|---|---|---|---|
8-MMMM8M8 | M | M | MM8Me | 88 (8.88 eee%), MMMM (88 eee%), MeMMe (8.8 eeeee), MMM, 888 °M, 88 e | – | 88 | [88] |
8-MMMM8M8 | M | M | Me | 88 (8.8 eee%), MeMMe (8.8 eeeee), MMMM (88 eee%), MMM, 888 °M, 8.8 e | 8:88e | 88 | [88] |
8-MeM8M8 | M | M | 8-MeMM8M8 | Me(MMe)8 (8.8 eee%), eeeeee (8 eee%), MeMMe (8.8 eeeee), MMM, 888 °M, 88 e | 88:8e | 88 | [88] |
8-MeM8M8 | M | M | Me | 88 (8.8 eee%), MeMMe (8.8 eeeee), MMMM (88 eee%), MMM, 888 °M, 8.88 e | 8:88e | 88 | [88] |
8-MeM8M8 | M | M | Me | Me/eeeeeeee (MeM) (88 eee), Me(MM)8 (8.8 eeeee), MMM, 888 °M, 8 e | – | 88 | [88] |
Me | M | M | MM8Me | Me8(eee)8 (8.8 eee%), e-Me8M (8 eee%), Me8MM8 (8.8 eeeee), eeeeeee, 888 °M, 88 e | – | 88 | [88] |
Me | M | M | MM8Me | 88 (8 eee%), Me8MM8 (8.8 eeeee), eeeee eeeeee 88, 888 °M, 8 e | – | 88 | [88] |
Me | M | Me | MM8Me | Me[M(e-Me)8]8 (8.8 eee%), Me8MMe (8.8 eeeee), eeeeeee, 888 °M, 88 e | – | 88 | [88] |
Me | M | M | Me | Me8(eee)8 (8.8 eee%), e-Me8M (8 eee%), Me8MM8 (8.8 eeeee), eeeeeee, 888 °M, 88 e | – | 88 | [88] |
Me | M | M | Me | MeMe8(MMe8)8 (8.8 eee%), Me8MM8 (8 eeeee), eeeeeee, 888 °M, 88 e | 88:8e | >88 | [88] |
8,8-Me8M8M8 | M | Me | MM8Me | Me8(eee)8 (8.8 eee%), [e-Me8MM]MM8 (8 eee%), Me8MMe (8.8 eeeee), eeeeeee, 888 °M, 88 e | >88:8e | 88 | [88] |
e Meeee (α-eeeeeee/β-eeeeeee).
e eeeee = 8,8-eee(eeeeeeeeeeeeeeeeeeee)eeeeee.
e Meeee (M/M).
Meeeeeeeeeee Meeeeeeee
Meeeee (M)-8-(8-Meeeeeeeeeee)eee-8-eeeeee (88, M8 = 8-Mee; M8 = Me; MMM = MM8Me):[88]
M eeeeeee ee Me(MMe)8 (88 ee, 8.8 eeee), 8-eeeeeeeeeee (88 eeee), eeeeee (M)-eee-8-eeeeee (88 eeee), eee Meeeeeeee MMM-888 (eeeee; 8 e) ee eeeee MMM (8 eM) eee eeeeeee ee 88 °M eee 8 e. Me eee eeeeee eee eeeeeeee ee eeeeee eee eeeee, eeeee eee eeeeee eeee Me8M. Mee eeeeeee eeeee eee eeeeeee eeee M8M eee eeeeeeeee eeee Me8M. Mee Me8M eeeee eee eeeeee eeee M8M eee eeeee (Me8MM8). Meeeeee ee Me8M eeeeeeeee eee eeeee eeeeeee, eeeee eee eeeeeeee ee eeeeeeeeeeeeeeeee; eee eeeeeeeee eeeeee eeeeee eee eeeeeeee ee eeeeeee eeeeeee e eeeeeeeeeeeeee eeeeee (eeeeee eee, eeeeeeeee eeeee); eeeee: 88%.
Meeee (M)-8-(8-Meeeeeeeeeeee)eeeeeeee (88, M8 = 8-MeMM8M8; M8 = M; MMM = MM8Me):[88]
Mee eeeeeeee ee eeeeeeeeeeee (8.88 e, 88 eeee), M8MM8 (8.88 e, 88 eeee), eee eeeee eeeeeeee (8.88 e, 88 eeee) ee 888 °M eeeeee 88 e ee eeeee MMM (88 eM) ee eee eeeeeeee ee [Me(η8-M8M8)Me]8 (8.888 eeee) eee 88 (8.888 eeee) eeeee eeeee eeeeeeee eee eeeeeeeeeeeee eeeeeeee eeeeeee eeeee eeeeeeeeee eeee MM8Me8, eeeeeeeeee, eeeeee (MeMM8), eeeeeeeeeee, eee eeeeeeeeee ee eeeeee eee (Me8M/eeeeeee 8:8); eeeee: 8.88 e (88%).
Meeeee (M)-Meeeeeeee (88, M8 = Me; M8 = M8 = M; MMM = MM8Me):[88]
Meeee ee eeeeeeeeee ee eeeee, e eeee ee eeeeeeeeeeeee (888 ee, 8.888 eeee) ee eeeeeee (8.8 eM) eee e eeee ee e-Me8M (88.8 ee, 8.888 eeee) ee eeeeeee (8.88 eM) eeee eeeee ee eeee ee e Meeeeee eeee eeeeeee eeee Me8(eee)8 (88.8 ee, 8.888 eeee), Me8MM8 (888 ee, 8.88 eeee), eee e eeeeeeee eeeeeee eee. Meeeee eeeeeeee (888 ee, 8.88 eeee) eee eeee eeeee ee eeeeeee, eee eee Meeeeee eeee eee eeeeee eee eeeeee ee e 888 °M eee eeee eee eeeeeee eee 88 e. Mee eeeeeee eee eeee eeeeee ee ee, eeeeeee eeee Me8M, eeeeeeee eeeeeee e eee ee Meeeee, eeeeeeeeeeee, eee eeeeeeee ee eeeee eeeeeeeeeeeeee (MeMMe/eeeeee 8:88); eeeee: 888 ee (88%).
References
[20] | Meeeeeee, M. M.; Meeeeeee, M.; Öeeee, M.; Meeeeeeee, M.-M.; Meeeeeeee, M.; Meeeee, M.; Meeeeee, M., Meeee. Meee., (8888) 888, 8888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 8888. |
[21] | Meeeee, M. M.; Mee, M.; Meeeeee, M.; Meeeeeee, M. M.; Meeeee, M., Mee. Meee., (8888) 8, 8888. |
[22] | Meeeeeee, M. M.; Meeeee, M.; Meeeeee, M.; Möeeee, M.; Meeee, M. M. M., Meeee. Meee., (8888) 888, 8888; Meeee. Meee. Mee. Me. Meee., (8888) 88, 8888. |
[23] | Meeeáe, Á.; Meee, M., Meeeeee, (8888), 8888. |
[24] | Meeeee, M. M.; Me, M. M., M. Mee. Meee., (8888) 88, 88. |
[25] | Meeeeeeeeee, M. M.; Mee, M.; Meeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[14] | Meee, M. M.; Meeeee, M. M., Me., M. Mee. Meee., (8888) 88, 8888. |
[26] | Meeeee-Meñee, M.; Méeee, M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[33] | Meeeeeeeeeee, M. M.; Meeeee, M. M.; Meeee, M. M.; Meee, M. M., Meeee. Meeeee., (8888) 88, 888. |
[27] | Meee, M.; Meee, M.; Meeeeeee, M., Meee. Meeeee. (Meeeeeeee), (8888), 888. |
[28] | Meee, M.; Meee, M.-M.; Mee, M.-M., Mee. Meee., (8888) 8, 8888. |
[29] | Meeeeeee, M.; Meeeeee, M.; Meeee, M.; Meeeee, M.; Meee, M.; Meeeee, M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[30] | Meeeeeeeeee, M. M.; Meeeee, M. M.; Mee, M.-M., M. Me. Meee. Mee., (8888) 888, 8888. |
[31] | Meee, M.; Mee, M.-M.; Meee, M.-M., Meeee. Meeeee., (8888) 88, 8888. |
[32] | Meeee, M.; Meee, M. M.; Meee, M.; Meeeeeee, M. M., Meee. Meeeee. (Meeeeeeee), (8888), 888. |
[34] | Meeeeee, M., M. Meeeeeeee. Meee., (8888) 888, 888. |
[39] | Meeeeeeeee, M.; Meeeee, M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[35] | Meeeeeeeee, M.; Meeeee, M.; Meeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[36] | Meeeee, M.; Mee, M.; Meeeeeeeeee, M. M.; Meeeeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[37] | Meeeeeee, M. M.; Meeeeeee, M. M.; Meeeeeeeeee, M. M.; Meeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[38] | Meeeeeeeeeeee, M.; Meeeeeeeee, M.; Meeeeee, M. M.; Meeee, M. M., Mee. Meee., (8888) 8, 8888. |
[40] | Meüeeeeeee, M.; Meeeeeee, M.; Meee, M. M.; Meeeee, M. M.; Meeeeeee, M. M., Meeeeeeeeeeeeee, (8888) 88, 8888. |
[46] | Meeeeeeee, M. M.; Me, M. M., Mee. Meee., (8888) 8, 8888. |
[41] | Mee-Meeee, M.; Meeeeee, M.; Meeee, M.; Meeeeeee, M., Meeeeeeeeeeeeee, (8888) 88, 8888. |
[42] | Meöeee, M. M.; Meeeee, M.; Möeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
[43] | Meee, M.-M.; Meeeeee, M.; Meeeeee, M. M., Mee. Meee., (8888) 8, 8888. |
[44] | Meeeee, M. M.; Me, M. M., Mee. Meeee., (8888) 88, 88. |
[45] | Me, M.; Mee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |