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2342449966
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A useful element of the O-carbamate is its proclivity for anionic ortho Fries rearrangement exposing a phenol that, upon triflation and Ni-catalyzed hydride reduction, also achieves its removal with retention of a new amide DMG for further DoM chemistry; see: Cai, X.; Brown, S.; Hodson, P.; Snieckus, V. Can. J. Chem. 2004, 82, 195 and refs cited therein.
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DoM chemistry of this function has, to the best of our knowledge, not been achieved. For cross-coupling chemistry, see: Tang, Z.-Y.; Hu, Q.-S. J. Am. Chem. Soc. 2004, 126, 3058 (Suzuki-Miyaura).
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33845550671
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In an attempt to trap the thermodynamically generated anion, treatment of 3 under Martin conditions (1g: LiTMP/TMSCl = 1:2.1:10) (Krizan, T. D.; Martin, J. C. J. Am. Chem. Soc. 1983, 105, 6155) led to SM (35%), 4e (41%), and 2,2,6,6-tetramethyl-1-(2-(trimethylsilyl)phenyl)-piperidine (19%) by GC analysis.
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Krizan, T.D.1
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4544344371
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49
-
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29844453785
-
-
note
-
Generalization of this result is being pursued.
-
-
-
-
50
-
-
2142705745
-
-
4, (IPr)Pd(allyl)Cl (Navarro, O.; Kaur, H.; Mahjoor, P.; Nolan, S. P. J. Org. Chem. 2004, 69, 3173),
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51
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0037146041
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3 (Fürstner, A.; Leitner, A.; Menendez, M. M.; Krause, H. J. Am. Chem. Soc. 2002, 124, 13856) catalysis was ineffective and led to recovery of starting material.
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Fürstner, A.1
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0035903607
-
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High activity of NiClCpIMes may be attributed to the presence of a low-valent electron-rich metal center owing to a strongly Lewis basic, electron σ-donating carbene ligand whose steric nature accelerates the reductive elimination step, see: Bohm, V. P. W.; Gstottmayr, C. W. K.; Weskamp, T.; Herrmann, W. A. Angew. Chem., Int. Ed. 2001, 40, 3387.
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Bohm, V.P.W.1
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54
-
-
29844456644
-
-
note
-
6 led only to the formation of p-isopropylanisole in low yield.
-
-
-
-
55
-
-
29844435430
-
-
note
-
4 in PhMe at 90°C for 24 h.
-
-
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