Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content.
1.1.1.1.1.1.2.11 Aryl Phosphate Electrophiles

DOI: 10.1055/sos-SD-207-00004

Guram, A. S.; Milne, J. E.; Tedrow, J. S.; Walker, S. D.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2013194.

Although aryl- and hetarylphosphonium salts are efficient cross-coupling partners with arylboronic acids, aryl phosphates have proven more challenging. Simple aryl diethyl phosphates can succumb to Suzuki–Miyaura reaction under nickel-catalyzed conditions.[‌150‌] As with other unactivated aryl electrophiles such as pivalates and sulfamates, dichlorobis(tricyclohexylphosphine)nickel(II) and potassium phosphate afford the highest yields of the diaryl products 116 (Table 41). Electron-deficient and electron-rich aryl phosphates undergo cross coupling with similar efficiency. Free aniline groups as well as 2-substitution are tolerated as part of the electrophile structure. Cyano groups are not tolerated, presumably due to competitive cross coupling with the nitrile functional group. Electron-rich boronic acids are generally preferred; however, with activated phosphates such as 2-naphthyl, electron-poor boronic acids undergo coupling in high yields.

Meeee 88 Meeeee-Meeeeeeee Meeeee–Meeeeee Meeeeeeee ee Meee Meeeeeeeee eeee Meeeeeeeeee Meeee[‌888‌]

Meeee Me8 Me8 Meeee (%) Mee
8 8-eeeeeeee 8-M8MM8M8 88 [‌888‌]
8 8-eeeeeeee 8-M8MM8M8 88 [‌888‌]
8 8-eeeeeeee 8-Mee 88 [‌888‌]
8 8-eeeeeeee 8-eeeeeeee 88 [‌888‌]
8 8-eeeeeeee Me 88 [‌888‌]
8 8-Mee 8-MeMM8M8 88 [‌888‌]
8 8-MM8M8 8-MeMM8M8 88 [‌888‌]
8 8-MeMM8M8 Me 88 [‌888‌]
8 8-MeM8M8 Me 88 [‌888‌]
88 8-MeM8MM8M8 Me 88 [‌888‌]
88 8-M8MM8M8 Me 88 [‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

Me eeee-eeeee Meeeeee eeee eeeeeeeeee MeMe8(MMe8)8 (8.888 eeee, 88 eee%), M8MM8 (8.88 eeee), eee MeM(MM)8 (8.888 eeee) eee eeeeeeeee eee eeeeee eeee eeeee (8 ×). Meeeeee eeeeeeeee eeeeeee (8.8 eM) eee eeeeeee 8-eeeeeeee eeeeeeeee (8.888 eeee) eeee eeeeeeeeeeee eeeee ee ee. Mee eeeeeee eee eeeeee eeee eeeeeeee ee 888 °M eee 88 e. Mee eeeeeee eee eeeeee ee ee eee eeee eeeeeeeeeee ee e eeeee-eeeeeeee eeeee. Meeeee eee (8.8 e) eee eeeee, eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee eeeeee e eeee-eeeeeee eeeeee. Meee eeeeee eee eeee eee-eeeeee eeee e eeeeee (eeeeee eee) eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee) ee eeeee eee eeeeeee ee e eeeee eeeeee; eeeee: 88.8 ee (88%).

References


Cookie-Einstellungen