Table 1.

Development of [Mn^III(ClPc)]-catalyzed intermolecular benzylic C–H amination.

Entry*	Sulfamate Ester	Oxidant	Catalyst	Temp	% yield (% rsm)
1	NH2Tces	Phl(OPiv)2	[FeIII(Pc)]SbF6	23 °c	0% (100%)
2	NH2Tces	Phl(OPiv)2	[MnIII(Pc)]SbF6	23 °c	trace (96%)
3†	NH2Tces	Phl(OPiv)2	[MnIII(Pc)]SbF6	23 °c	trace (95%)
4	NH2Tces	Phl(OPiv)2	[MnIII(BuPc)]SbF6	23 °c	trace (94%)
5‡	NH2Tces	Phl(OPiv)2	CoII(TPP)	23 °c	0%(99%)
6		Phl=NTces	[FeIII(Pc)]SbF6	23 °c	9%(85%)
7		Phl=NTces	[MnIII(tBuPc)]SbF6	23 °c	12%(88%)
8		Phl=NTces	[MnIII(Pc)]SbF6	23 °c	17%(83%)
9		Phl=NTces	[MnIII(ClPc)]SbF6	23 °c	53%(41%)
10		Phl=NTces	[MnIII(ClPc)]SbF6	40 °c	68%(32%)
11§		Phl=NTces	[MnIII(ClPc)]SbF6	40 °c	47%(49%)
12‖		Phl=NTces	[MnIII(ClPc)]SbF6	40 °c	42%(58%)
13¶		Phl=NTces	[MnIII(ClPc)]SbF6	40 °c	60%(24%)
14		Phl=NTces	[MnIII(ClPc)]Cl	40 °c	0%(100%)
15		Phl=NTces	AgSbF6	40 °c	trace(100%)
16		Phl=NTces	CoII(TPP)	40 °c	trace(95%)
17	NH2 Tces	Phl(OPiv)2	[MnIII(ClPc)]SbF6	40 °c	trace(87%)

^*Reaction conditions: 1 (0.2 mmol, 1 equiv), catalyst (10 mol%), AgSbF₆ (10 mol%), oxidant (2 equiv), C₆H₆ (0.5M), 5Å molecular sieves (40 mg), 8 h. Yields are of isolated products. Trace yield (<5%) and recovered starting material (rsm) are reported based on ¹H NMR analysis of the crude reaction using 1,3,5-trimethylbenzene as an internal standard.

^†2.2 equiv of MgO used as an additive in the reaction.

^‡A separate reaction with 1 (1 equiv), TrocN₃ (2 equiv), Co^II(TPP) (10 mol%), C₆H₆ (0.5M), 40 ˚C, 5Å molecular sieves (40 mg), 8 h resulted in 0% yield (88% rsm). TPP = tetraphenylporphyrin.

^§5 mol% catalyst used.

^‖1 equiv of PhI=NTces used.

^¶3Å molecular sieves used. 1,2-DCE used as solvent.