Science of Synthesis

Liu, S.; Xiao, J., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2013) 3, 226.

Following the observation that hydrogen-bond donors appear to promote the α-arylation of electron-rich alkenes,[‌30‌] Xiaoʼs group went on to demonstrate that palladium(II) acetate/1,3-bis(diphenylphosphino)propane-catalyzed α-arylation reactions can be readily carried out in hydrogen-bond-donating alcohols, which are inexpensive, environmentally benign, and readily available.[‌37‌,‌38‌] The reaction proceeds particularly well in ethylene glycol to give ketones ‌11‌ and also furnishes branched products with excellent selectivity. Selected examples of vinyl ethers reacting with aryl bromides are shown in ‌Scheme 16‌. Further studies have revealed that the palladium/1,3-bis(diphenylphosphino)propane catalysis in ethylene glycol is remarkably efficient, displaying high turnover frequencies and turnover numbers of up to 1.56 × 105 h−1 and 3.75 × 105, respectively.[‌39‌]

‌Meeeee 88‌ Meeeeeeee ee Meeee Meeeee ee Meeeeeee Meeeee[‌88‌]

‌Meeeeeeeeee 88‌

Me eeeee eeeeeee ee eeeeeeee ee eeeeeeee ee eeee eeeeee eee ee eeeeeeee eeeeeee eeeeeeeee ee eeeeeeeeeeee eeeee eeeeee. Me eeeee ee ‌Meeeee 88‌, eeeeee eeeeee ‌88‌ eee eeeeeeee ee eeee eeeeee eeeeeeeee eee eeeeeeeee/8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee-eeeeeeeee eeeeeeeee ee eeeee eeeee eeeee eeee eeee eeeeeeee ee eeeeeeee eeeeee (eeeeeee eeeeee eeeeee).[‌88‌] Meee eeeeeeee eee eeee ee eeeeeee eee ee eeeee eeeee, eeee ee eeeeeee-8,8-eeee eee eeeeeee-8,8-eeee, eeeeeeeee e eee eeeeee eee eeeeeeeeeeee eeeeee eeeeee.

‌Meeeee 88‌ Meeeeeeee ee Meeeee Meeeee eee eee Meee Meeeeeeee ee Meeee Meeee Meeee ee Meeeeeee Meeeee[‌88‌]

‌Meeeeeeeeee 88‌

Me8	Meeee (%)	Mee
Me	88	[‌88‌]
8-MM8M8	88	[‌88‌]
8-MeM8M8	88	[‌88‌]
8-MeM8M8	88	[‌88‌]
8-MeMM8M8	88	[‌88‌]
8-Mee	88	[‌88‌]
8-MeM8M8	88	[‌88‌]
8-Mee	88	[‌88‌]
8-M8MM8M8	88	[‌88‌]
8-Mee	88	[‌88‌]
8-eeeeeeee	88	[‌88‌]
8-eeeeeeee	88	[‌88‌]
	88	[‌88‌]

Meee eeeeeeeeeeeee, eee eeeeeee eee eeee eeeeeeeeeeee eeeeeeee ee eeeeeeee eeee eeeeeee eeee eeeeeeeee, eeeee eee eeee eeee eeeeeee ee α-eeeeeeeee. Meeee ee eee eeeeee ee eeeeeeee-eeee eeeeeeee ee 8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee, 8,8-eee[eee(8-eeeeeeeeeeeee)eeeeeeeee]eeeeeee (‌88‌), Meeeʼe eeeee eee eeeee eeee eeeeeeee-eeee eeeeeee eee ee eeeeeeee eeee e eeee eeeee ee eeee eeeeeeeee ee eeee eeeeeeee eeeeeee ‌88‌ ee eeeeeeee eeeeee ee e eeeeee α-eeeeeeeeeeeeee eeeeee (‌Meeeee 88‌).[‌88‌] Meee eee eeeeeeee-eeee eeeeee ‌88‌ eee eeeeeeee eeeeee eee eeeeeeeee eee eee eeeeeeeee, eeee eee eeeeee eeeeeeeeeeee eee eeee-eeeeeeee eeeeeeeee eeeeeeee eeee eeeee eee eeeeee eeeeeeeeee eee eeeeeeeeeeee ee eeeeeeee eeee eeeeeeeee. Meee, eeeeee eeeeeeeee eeeeee eeee eee eeeeeeee ee eee ee eeeeeeeeeeeeeeeee ee eeeeeeee eeeeeeeee. Meeeeee eeeeeeeeee eeeeee eeeeeeeeeeee eeee eeeeeee eeeee ee eee eeeeeeeee, eeeeeee eeee eeeeeeee eeeeee eeeeeeeeeeee ee eee eeeeeeeeee eeeee ee eee eeeeeeeee eeeeeeee eeeeeeee, eeeeeeee eee eeeeee eeeeeee eee eeeeeee eeeeeeeee eee eeeeeeee eeee.[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee Meeee Meeeee eeee Meee Meeeeeeee ee Meeeeeee Meeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Me(MMe)8 (8 eee%) eee ‌88‌ (8 eee%) eeee eeee.

Meee 8-eeeeeeeeeeeeeeeee eee eeee ee eee eeeeeeeee eeeeeeee, eeeee-8-eeee ‌88‌ eee ee eeeeee eeeeeeee eee eeee eeeeeeee. M eeeeeee ee eeeeeeee eeee eeee eeeeeeee, eeeeeeeee eeee eeee eeeeeeee eee eeee eeeeeeeee (‌Meeeee 88‌). Me eee eeee ee eee eeeeee, eeeeeeeee/8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee ee eeeeeeeeee, eeeeeee eee eee eeeeeeeee, ‌88‌ ee eee eeeeee ee eeeeee. Meeee eeeeeeeee eeeeeee eee eee Meee eeeeeeeee, eeeeeeee ee ee eeeee-eeee eeeeeeeeeeeeee eeeeeeeeeeee eeeeee ee eee eeeeeeee eeeee ee eee eeeeeeee eeee eeeeeeeeeeeee.[‌88‌] Meeeeeee eeeeee ee eeeeeeee ee eeee e eeee ee eeee eee Meee eee eee eeeeeeeeeee eeeeeeeee.

‌Meeeee 88‌ Meeeeeeee ee Meeee Meeeee eeee 8-Meeeeeeeeeeeeeeee ee 8-Meeeeeeeee Meeeeee ee Meeeeeee Meeeee[‌88‌]

‌Meeeeeeeeee 88‌

e Meeee (eeeeeeee/eeeeee) 8:8.8.

‌Meeeeeeeeee 88M‌

e Meeee (eeeeeeee/eeeeee) 8:8.8.

‌Meeeeeeeeee 88M‌

e Meeee (eeeeeeee/eeeeee) 8:8.8.

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Me eeee-eeeee, eee-eeeeee, eeeee-eeeeeeee eeeee eeeeeeeeee e eeeeeee eee eee eeeeeee eeee eee eeee eeeeeee (8.8 eeee), Me(MMe)8 (88 ee, 8.88 eeee), eeee (88 ee, 8.8 eeee), eee eeeeeeee eeeeee (8 eM) eeeee M8 ee ee. Meeeeeeee eeeee eeeeeeeee eeeeee, eee eeeee eeeee (8.8 eeee) eee Me8M (8.8 eeee) eeee eeeeeeeeeeee eeeeeeee. Mee eeeee eee eeeeee ee ee eee eeee, eee eee eeeeeee eee eeeeeee eee eeeeee ee 888 °M eeeeeeeee. Mee eeeee eee eeeeeee eeee eee eee eeee eee eeeeeee ee eeee ee ee. M eeeee eeeeee eee eeee eeeee eee eeeeeeee ee MMM. Meee eee eeeeeeee eee eeeeeeee, 8% ee MMe (8 eM) eee eeeee eee, eeeee eeeeeeee eee 8.8 e, MM8Me8 (8 eM) eee eeeee. Meeee eeeeeeeeee ee eee MM8Me8 eeeee, eee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M eeeee eeeeeeeeee eee eeeeeeee, eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee eeeee e eeeeee eee eeeeee Meeeeee eeeee eeeee MM8Me8 ee eee eeeeee.

8-(8-Meeeeeeeeeee)-8-eeeeee-8,8-eeeeeeeee (‌88‌, Me8 = 8-MeM8M8); Meeeeee Meeeeeeee:[‌88‌]

Me eeee-eeeee Meeeeee eeee eee eeeeeee eeee 8-(8-eeeeeeeeeee)eeeeeeee (888 ee, 8 eeee) eee eeeeeeee eeeeee (8 eM). Mee eeeee eee eeeeeeeee eee eeeeeeeeee eeee M8 (8 ×). Me8M (8.8 eM, 8 eeee) eee e Me(MMe)8/eeee eeeee eeee [8 eM; eeeeeeeeee Me(MMe)8 (8.888 eeee, 8.8 eee%) eee eeee (8.88 eeee)] eeee eeeee eee eeeeeee eee eee eeee eee eeeeee ee e eeeeeeee eeeeeee (eeeee eeeeeeeeeee 888 °M). Mee eeeeeee eee eeeeeeeeee eeeeeee eee 8–8 eee, eeeee eeeee eeee eeeee eeeee eeeee (8.8 eM, 8 eeee) eee eeeeeeee. Mee eeeeeeee eee eeeeeeeee ee MMM eeeee ee eeeee ee eeeeeeee eeeeeeee ee eee eeeeeeeeeeee eeeeeeee eeee eeeee eeeeeeee. Mee eeeee eee eeeeeee ee eeee ee ee eee M8M (88 eM) eee eeeee. Mee eeeeeee eeeee eee eeee eeeeeeeee eeee Me8M (8 × 88 eM) eee eee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M (88 eM). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:8); eeeee: 888 ee (88%).

8-Meeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Me eeee-eeeee eeeeeeee eeeeeeee eeee eeeeeeeeee e eeeeeee eee eee eeeeeee eeee eee eeee eeeeeeee (8.8 eeee), Me(MMe)8 (8.88 eeee), eeeeee ‌88‌ (8.888 eeee), eee MMM (8.8 eeee). Meeee eeeeeeeee eeee M8 (8 ×), eeeeeeee eeeeee (8 eM) eee eee eeeee eeeee (8.8 eeee) eeee eeeeeeee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeeeee eeeeeee ee 888 °M eee eee eeeeeeeeeee eeee eee, eeeee eeeeeee ee ee, 8 M ee MMe (8 eM) eee Me8M (88 eM) eeee eeeee eee eee eeeeeee eee eeeeeee eee 8 e. Meeee eeeeeeeeee ee eee Me8M eeeee, eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee, eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:88 ee 88:88).

8-Meeeeeeeeeee-8-eeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

Me eeee-eeeee eeeeeeee eeeeeeee eeee eeeeeeeeee e eeeeeee eee eee eeeeeee eeee eee eeee eeeeeee ee eeee eeeeeeee (8.8 eeee), Me(MMe)8 (8.88 eeee eee eeee eeeeeeee; 8.88 eeee eee eeee eeeeeeeee), eee eeee (8.888 eeee) ee ‌88‌ (8.88 eeee). Meeee eeeeeeeee eeee M8 (8 ×), eeeeeeee eeeeee (8 eM), eee eeeee eeeee (8.8 eeee), eee Me8M (8.8 eeee) eeee eeeeeeee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeeeee eeeeeee ee 888 °M (eeee eeeeeeee) ee 888 °M (eeee eeeeeeeee) eee 88 e. Meeee eeeeeee ee ee, 8 M ee MMe (8 eM) eee MeMMe (88 eM) eeee eeeee eee eee eeeeeee eee eeeeeee eee 8 e. Meeee eeeeeeeeee ee eee MeMMe eeeee, eee eeeeeee eeeee eee eeeeeeeee eeee MeMMe (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee, eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:8 ee 8:8).

References