Table 1.

Benzylic oxidation of unactivated hydrocarbons.

						product distribution (%)
entry	substrate	radical initiator	catalysta	conditions	conv (%)	hydroperoxide	alcohol	carbonyl	ref
1	Toluene	HPPDO	CuCl2	4.9 atm O2,	71			4:94b	43
2	p-Xylene	none	CuBr	cat LiBr, 7.8 atm O2, 150 °C, 2 h	20			88c	31
3	Ethylbenzene	aldehyde	CuCl2, 18-Crown-6	1 equiv MeCHO, 1 atm O2, CH2Cl2, 24 h, rt	8.5		24	76	34a
4		peroxide	[CuI(pyr)(tpb)]	1 mol% TBHP, 1 atm O2, 1:2 AcOH:pyr, rt, 24 h	5.8		1	99	35
5	Indane	aldehyde	Cu(OAc)2	1 equiv MeCHO, MeCN/CH2Cl2, rt, 36 h	35		23	77	42
6		aldehyde	Cu(TPIP)2	6 equiv isobutyraldehyde, O2 DCE, rt, 4 h	49	63	12	24	28
7		aldehyde	CuCl2, 18-Crown-6	1 equiv MeCHO, 1 atm O2, CH2Cl2, 70 °C, 24 h, rt	36		31	69	34a
8	Tetralin	none	[Cu(CTZ)2Cl2]2	35 atm air, 100 °C, 9 h	57		25	75	36
9		none	Cu(2-pymo)2	1 atm air, 90 °C, 48 h	52	2	26	71	37
10		aldehyde	CuCl2, 18-Crown-6	1 equiv MeCHO, 1 atm O2, CH2Cl2, 70 °C, 24 h, rt	37		25	75	34a
11		peroxide	Cu(OH)2	cat H2O2, 14.6 atm O2, i-PrOH/DMA, cat FeCl3, 90 °C, 30 min	49		21	79	38
12	Cumene	none	Cu(OAc)2 on Chelex	0.9 atm O2, 80 °C, 12 h	5.4	99			33
13		AIBN	Cu(acac)2, NHPI	3 mol% AIBN, 1 atm O2, MeCN, 60 °C, 4.5 h	72	19	63	15	30
14		ACBN	Cu(acac)2, NHPI	3 mol% ACBN, 1 atm O2, benzonitrile, 90 °C, 3 h	29	4	26	57	30
15	Cyclohexyl-benzene	none	α,β,γ,δ-tetraanthracyl-porphinato-copper(II)	13.6 atm O2, 115 °C, 4.9 h	14	99d			39, 40

^aSee Chart 1 for ligand structures.

^b4:94 benzaldehyde:benzoic acid.

^cAcid and diaryls were the other major products.

^dIncludes oxidation products at other positions of the cyclohexyl ring.