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Guram, A. S.; Milne, J. E.; Tedrow, J. S.; Walker, S. D., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2013) 1, 94.
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.
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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] |
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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
[150] | Meee, M.; Meeee, M.; Me, M.; Meee, M.; Me, M.; Meee, M.; Meeee, M.-M., M. Mee. Meee., (8888) 88, 8888. |