Table 5.

Glaser Hay dimerization reactions.

entry	substrate	conditions	yield(%)	ref
1		8 mol% Cu(OAc)2·H2O, TMEDA, acetone, air, rt, 2h	91	145
2		CuCl, TMEDA, O2, MeOH, THF	81a	130
3		5 mol% CuI, TMEDA, DME, O2, 55 °C, overnight	≥90	146
4		15 mol% CuCl, 30 mol% pyridine, MeOH, O2, rt	Ar1 = 91	147
			Ar2 = 93
			Ar3 = 75
5		10 mol% CuCl, TMEDA, MeOH, air, rt, 24 h	60–72	148
6		10 mol% CuI, TMEDA, O2, acetone, rt, 3 h	84–100	149
7		CuCl, TMEDA, air, CHCl3	94	150
8		10 mol% CuI, 20 mol% TMEDA, acetone, air, rt	67	151
9		3 equiv CuCl, TMEDA, acetone, O2, 1 h, rt	76 (n = 3, R = Me)	152
			86 (n = 3, R = H)
			95 (n = 6, R = H)
10		4 mol% CuCl, TMEDA, acetone, O2, rt, 6 h	84	153
11		14 mol% CuCl, TMEDA, acetone, O2, rt, 4 h	52	154
12		CuCl, TMEDA, CH2Cl2, O2	50a (n = 2)	155
			44a (n = 3)
			19a (n = 4)
13		CuCl, TMEDA, CH2Cl2, O2	92 (n = 2)	156
			66 (n = 3)
			97 (n = 4)
14		40 mol% CuCl, pyridine, air, 24 h, rt	95	157
15		25 mol% CuCl, pyr, air, 40 °C, 1.5 h	60	158
16		1 equiv CuCl, TMEDA, CH2Cl2, air, 30 °C, 2–4 h	99	159
17		6.3 equiv CuCl, TMEDA, CH2Cl2, air, rt, 12 h	91	160
18		CuCl, TMEDA, CH2Cl2, air	68	161
19		CuCl, TMEDA, air, acetone, rt, overnight	43	162
20		12 mol% CuCl, TMEDA, chlorobenzene, O2, rt, 3d	50	163
21		4.8 equiv CuCl, TMEDA, acetone, O2, rt, 48 h	88	164
22		CuCl, TMEDA, CH2Cl2, O2, rt, 24 h	91	165
23		30 mol% CuCl, O2, DMF, rt, 12 h	26	166
24		CuCl, TMEDA, O2, CH2Cl2, rt	99	167
25		1 equiv CuCl, TMEDA, CH2Cl2, O2, rt, 4 h	60	168
26		5 mol% CuCl, TMEDA, toluene, 65 °C, 1.5 h	45	169
27		catalytic CuCl(OH)·TMEDA, CH2Cl2, O2, rt, overnight	57	170
28		20 mol% CuCl, pyr, O2, rt, 24 h	86	171
29		30 mol% CuCl, TMEDA, O2, acetone, rt, 48 h	89	172
30a		4 equiv CuI, TMEDA, CH2Cl2, O2, rt	96a (n= 1)	173
			78a (n = 2)
			68a (n = 3)
31		CuCl, TMEDA, CH2Cl2, rt, O2	R1 = 87	174
			R2 = 68
32		4 equiv CuCl, TMEDA, CH2Cl2, O2, rt	32a (n =2)	175
			20a (n = 3)
			34a (n = 4)
			34a (n = 5)
			22a (n = 7)
			(cyclic dimers)
33		CuCl, TMEDA, O2, CH2Cl2	R1 = 70	176
			R2 = 86
			R3 = 54
34		CuCl, TMEDA, air, CH2Cl2, rt, 6 h	70	177
35		5 equiv CuCl, TMEDA, O2, CH2Cl2	64a	178
36		CuCl, TMEDA, O2, CH2Cl2	R1 = 65a	132
			R2 = 55a
			R3 = 69a
37		CuCl, TMEDA, air, CH2Cl2, rt	51a	132
38		CuCl, TMEDA, air, CH2Cl2	48a	132
38		10 equiv CuCl, 5 equiv CuCl2, O2, DMF, rt, 4d	82	179
39		CuCl, TMEDA, air, DCE, 50 °C	91	180
40		2.8 equiv CuCl, TMEDA, CHCl3, O2, rt	68	181
41		50 mol% CuCl, TMEDA, air, CH2Cl2, rt	86	182
42		CuCl, TMEDA, acetone, air, 17 h, rt	93	183
43		2.6 equiv CuCl, TMEDA, CH2Cl2, air, overnight	93	184
44		10 mol% CuCl, TMEDA, O2, isopropanol, acetone, rt, 5 h	81	185
45		20 mol% CuCl, 20 mol% TMEDA, acetone, O2, 35 °C, 1.5 h	82	186
46		14 mol% CuCl, pyr, air, 40 °C, 6.5 h	36	187
47		20 mol% CuCl, TMEDA, DME, rt, air, overnight	59	188
48		CuCl, TMEDA, O2, CH2Cl2, rt	81	189
49		10 mol% CuI, pyrrolidine, air, rt	48–90	190
50		1.1 equiv CuCl, air, TMEDA, acetone, rt, 5 h	64	191
51		3.6 equiv CuCl, TMEDA, CH2Cl2, O2, rt, overnight	83	192
52		2.5 equiv CuCl, TMEDA, CH2Cl2, air, rt, 15 min	yield not reported	193
53		0.5 mol% CuCl, DBU, pyridine, O2, 3 h, 45 °C	96	194
54		1 equiv CuCl, TMEDA, CH2Cl2, air, 4 h, rt	100	195
55		2 equiv CuCl, TMEDA, O2, H2O, rt 3 d	68	196
56		CuCl, TMEDA, DMF, O2, 40 °C, 4 h	99	197
57		CuCl, TMEDA, acetone, O2, rt, 4h	96	198
58		30 mol% CuCl, TMEDA, DMF, O2, 40 °C, 2 h	86 (X = O)	199
			83 (X = S)
59		42 mol% CuCl, TMEDA, acetone, O2, rt,	25	200
60		50 mol% CuCl, TMEDA, acetone, O2, 4 h, rt	95	201
61		superstoich. CuCl, TMEDA, acetone, air, rt, 1.5 h	60 (R = Cr)	202
			55 (R = W)
62		1 equiv CuCl, TMEDA, CH2Cl2, O2, 4Å mol sieves, 12 h, rt	75	203
63		1.05 equiv CuCl, DBU, pyridine O2, 45 °C, 2h	>72 (n = 2)	204
			>87 (n = 4)
			(cyclic dimer)
64		11 mol% CuCl, pyridine, O2, rt, 30 h, 32%	32 (cyclic dimer)	205
65b		7.5 equiv CuI, TMEDA, CH2Cl2, air, rt	51 (cyclic dimer)	206
66		CuCl, TMEDA, air, CH2Cl2, rt, 18 h	72 (mixture of four diastereomer ic cyclic dimers)	207
67		2 equiv CuCl2, TMEDA, acetone, O2, rt, 5 h	32 (cyclic dimer)	208
68		CuCl, TMEDA, CH2Cl2, air, 0 °C	71a (cyclic trimer)	209

^aSubstrate coupled directly after deprotection from silyl-protected precursor.

^bFor cyclodimerization of a similar substrate with excess copper catalyst see ref 210.