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3.12.1.1.1 Reaction of Electron-Poor Alkenes

DOI: 10.1055/sos-SD-203-00304

Shibasaki, M.; Ohshima, T.; Itano, W.Science of Synthesis: Stereoselective Synthesis, (20113485.

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 13). Substrates that are reactive in the oxidative addition, e.g. aryl iodides and activated aryl bromides, react smoothly under the classical MizorokiHeck 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 (0.050.5mol%), 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 MizorokiHeck 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 MeeeeeeeMeee Meeeeeee ee Meee Meeeeee eeee Meeeeeee-Meee Meeeeee[‌88‌,‌88‌‌88‌]

M8 M8 MMM Meeeeeeeee Meeee (%) Mee
8-M8MM8M8 M MM8Me MeMe8(MMe8)8 (8eee%), Me8M (8 eeeee), MeMM, 88°M, 88e 88 [‌88‌]
Me M MM8Me Me(MMe)8 (8eee%), Me8M (8 eeeee), 888°M, 8e 88 [‌88‌]
Me M MM8Me 88 (8.8eee), Me8M (8.8 eeeee), MMM, 888°M, 88e 888 [‌88‌]
Me M MM8Me Me(eee)8 (8.888eee%), 88 (8.888eee%), Me8M (8.8 eeeee), MMM, 888°M, 88e >88 [‌88‌]
Me M MM8Me Me/M (8.888eeee), Me8M (8.8 eeeee), eeeee eeeeee 88, 888°M, 88e 88 [‌88‌]
Me M MM8e-Me 88 (8.8eee%), Me8MM8 (8.8 eeeee), MMM, eeeee eee, 888°M, 88e 88 [‌88‌]
Me M MM Me(MMe)8 (8eee%), MMMM (88eee%), MeMMM8 (8 eeeee), M8M, 8888°M, 88e 88 [‌88‌]
Me M Me 88 (8eee%), MeMMe (8.8 eeeee), MMM, eeeee eee, eeeeee, 8e 88 [‌88‌]
Me M 8-M8MM8M8 Me(MMe)8 (8eee%), Me8M (8 eeeee), 888°M, 8e 88 [‌88‌]
8-Mee M MM8M Me(MMe)8 (8eee%), Meeeeeeee MMM-888 eeeee (888e·eee8), MMM, 88°M, 8e 88 [‌88‌]
8-Mee Me MM8M Me(MMe)8 (8eee%), Meeeeeeee MMM-888 eeeee (888e·eee8), MMM, 88°M, 8e 88 [‌88‌]
8-Mee Me MM8Me Me(MMe)8 (8eee%), Meeeeeeee MMM-888 eeeee (888e·eee8), MMM, 88°M, 8e 88 [‌88‌]
8-Mee Me MM8eMe Me(MMe)8 (8eee%), Meeeeeeee MMM-888 eeeee (888e·eee8), MMM, 88°M, 8e 88 [‌88‌]
8-Mee M Me Me(MMe)8 (8eee%), Meeeeeeee MMM-888 eeeee (888e·eee8), MMM, 88°M, 8e 88 [‌88‌]
8-MeMM8M8 M Me Me(MMe)8 (8eee%), Meeeeeeee MMM-888 eeeee (888e·eee8), MMM, 88°M, 8e 88 [‌88‌]

Meeee 8 MeeeeeeeMeee Meeeeeee ee Meee Meeeeeee eeee Meeeeeee-Meee Meeeeee[‌88‌,‌88‌,‌88‌,‌88‌‌88‌]

M8 M8 MMM Meeeeeeeee Meeee (%) Mee
8-M8MM8M8 M MM8Me Me(MMe)8 (8.888eee%), (8-Mee)8M (8.888eee%), MeMMe (8.8 eeeee), MMM, 888°M, 8e 88 [‌88‌]
8-M8MM8M8 M MM8Me [Me(η8-M8M8)Me]8/88 (8:8; 88eee), M8MM8 (8 eeeee), MMM, 888°M, 88e 888 [‌88‌]
8,8-(M8M)8M8M8 M MM8Me [Me(η8-M8M8)Me]8/88 (8:8; 8.88eee), M8MM8 (8 eeeee), MMM, 888°M, 88e 888 [‌88‌]
8-MeM8M8 M MM8Me [Me(η8-M8M8)Me]8/88 (8:8; 8eee), M8MM8 (8 eeeee), MMM, 888°M, 88e 88 [‌88‌]
8-MMMM8M8 M MM8Me 88 (8eee), MeMMe (8.8 eeeee), MMM, 888°M, 88e >88 [‌88‌]
8-eeeeeeee M MM8Me [Me(η8-M8M8)Me]8/88 (8:8; 888eee), M8MM8 (8 eeeee), MMM, 888°M, 88e 88 [‌88‌]
8-eeeeeee M MM8Me [Me(η8-M8M8)Me]8/88 (8:8; 88eee), M8MM8 (8 eeeee), MMM, 888°M, 88e 88 [‌88‌]
Me M MM8Me 88 (8eee), Me8MM8 (8.8 eeeee), MMM, 888°M, 88e 88 [‌88‌]
Me M MM8Me 88 (8.8eee%), Me8MM8, MMM, 888°M, 88e 888 [‌88‌]
Me M MM8Me Me(eee)8 (8.8eee%), 88 (8.8eee%), Me8M (8.8 eeeee), MMM, ee, 88e 88 [‌88‌]
Me M MM8Me [Me(η8-M8M8)Me]8/88 (8:8; 888eee), M8MM8 (8 eeeee), MMM, 888°M, 88e 88 [‌88‌]
8-MeMM8M8 M MM8Me [Me(η8-M8M8)Me]8/88 (8:8; 888eee), M8MM8 (8 eeeee), MMM, 888°M, 88e 88 [‌88‌]
Me M Me 88 (8eee%), MeMMe (8.8 eeeee), MMM, eeeee eee, eeeeee, 8e >88 [‌88‌]
Me M Me Me(MMe)8 (8eee%), Me8M (8 eeeee), MMM (MM 8888), 88°M, 88e 88 [‌88‌]
Me M Me [Me(η8-M8M8)Me]8/88 (8:8; 88eee), M8MM8 (8 eeeee), MMM, 888°M, 88e 88 [‌88‌]
8-MeMM8M8 M Me Me(MMe)8 (8eee%), Me8M (8 eeeee), MMM (MM 8888), 88°M, 88e 88 [‌88‌]
8-MeMM8M8 M Me [Me(η8-M8M8)Me]8/88 (8:8; 88eee), M8MM8 (8 eeeee), MMM, 888°M, 88e 88 [‌88‌]

Meeee 8 MeeeeeeeMeee Meeeeeee ee Meee Meeeeeeee eeee Meeeeeee-Meee Meeeeee[‌88‌,‌88‌,‌88‌‌88‌]

M8 M8 M8 MMM Meeeeeeeee Meeeeee Meeee Meeee (%) Mee
8-MMMM8M8 M M MM8Me 88 (8.88eee%), MMMM (88eee%), MeMMe (8.8 eeeee), MMM, 888°M, 88e 88 [‌88‌]
8-MMMM8M8 M M Me 88 (8.8eee%), MeMMe (8.8 eeeee), MMMM (88eee%), MMM, 888°M, 8.8e 8:88e 88 [‌88‌]
8-MeM8M8 M M 8-MeMM8M8 Me(MMe)8 (8.8eee%), eeeeee (8eee%), MeMMe (8.8 eeeee), MMM, 888°M, 88e 88:8e 88 [‌88‌]
8-MeM8M8 M M Me 88 (8.8eee%), MeMMe (8.8 eeeee), MMMM (88eee%), MMM, 888°M, 8.88e 8:88e 88 [‌88‌]
8-MeM8M8 M M Me Me/eeeeeeee (MeM) (88eee), Me(MM)8 (8.8 eeeee), MMM, 888°M, 8e 88 [‌88‌]
Me M M MM8Me Me8(eee)8 (8.8eee%), e-Me8M (8eee%), Me8MM8 (8.8 eeeee), eeeeeee, 888°M, 88e 88 [‌88‌]
Me M M MM8Me 88 (8eee%), Me8MM8 (8.8 eeeee), eeeee eeeeee 88, 888°M, 8e 88 [‌88‌]
Me M Me MM8Me Me[M(e-Me)8]8 (8.8eee%), Me8MMe (8.8 eeeee), eeeeeee, 888°M, 88e 88 [‌88‌]
Me M M Me Me8(eee)8 (8.8eee%), e-Me8M (8eee%), Me8MM8 (8.8 eeeee), eeeeeee, 888°M, 88e 88 [‌88‌]
Me M M Me MeMe8(MMe8)8 (8.8eee%), Me8MM8 (8 eeeee), eeeeeee, 888°M, 88e 88:8e >88 [‌88‌]
8,8-Me8M8M8 M Me MM8Me Me8(eee)8 (8.8eee%), [e-Me8MM]MM8 (8eee%), Me8MMe (8.8 eeeee), eeeeeee, 888°M, 88e >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 (88ee, 8.8eeee), 8-eeeeeeeeeee (88eeee), eeeeee (M)-eee-8-eeeeee (88eeee), eee Meeeeeeee MMM-888 (eeeee; 8e) ee eeeee MMM (8eM) eee eeeeeee ee 88°M eee 8e. 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 (8.88e, 88eeee), M8MM8 (8.88e, 88eeee), eee eeeee eeeeeeee (8.88e, 88eeee) ee 888°M eeeeee 88e ee eeeee MMM (88eM) ee eee eeeeeeee ee [Me(η8-M8M8)Me]8 (8.888eeee) eee 88 (8.888eeee) 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: 8.88e (88%).

Meeeee (M)-Meeeeeeee (88, M8=Me; M8=M8=M; MMM=MM8Me):[‌88‌]

Meeee ee eeeeeeeeee ee eeeee, e eeee ee eeeeeeeeeeeee (888ee, 8.888eeee) ee eeeeeee (8.8eM) eee e eeee ee e-Me8M (88.8ee, 8.888eeee) ee eeeeeee (8.88eM) eeee eeeee ee eeee ee e Meeeeee eeee eeeeeee eeee Me8(eee)8 (88.8ee, 8.888eeee), Me8MM8 (888ee, 8.88eeee), eee e eeeeeeee eeeeeee eee. Meeeee eeeeeeee (888ee, 8.88eeee) eee eeee eeeee ee eeeeeee, eee eee Meeeeee eeee eee eeeeee eee eeeeee ee e 888°M eee eeee eee eeeeeee eee 88e. 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: 888ee (88%).

References


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