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. Author manuscript; available in PMC: 2015 Apr 14.
Published in final edited form as: Adv Synth Catal. 2014 Jan 31;356(6):1359–1369. doi: 10.1002/adsc.201300904

Table 1. Optimization of aerobic dehydrogenative olefination of enaminones.

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Entry[a] [Pd] (mol %) [Cu] (mol %) Atm. Additive (mol %) Solvent Temp (°C) Yield (%) [b]
1 Pd(OAc)2 (10) Cu(OAc)2 (200) N2 KTFA (100) DMF 80 87 (81[c])
2 Pd(OAc)2 (10) – air KTFA (100) DMF 80 27
3 Pd(OAc)2 (10) – O2 KTFA (100) DMF 80 44
4 Pd(OAc)2 (10) Cu(OAc)2 (20) O2 KTFA (100) DMF 80 41
5 Pd(OAc)2 (5) Cu(OAc)2 (5) O2 catechol (10) DMF 80 40
6 Pd(OAc)2 (10) Cu(OAc)2 (10) O2 catechol (20) DMF rt 78
7 Pd(OAc)2 (10) Cu(OAc)2 (10) air catechol (20) DMF rt 66
8 Pd(OAc)2 (10) Cu(OAc)2 (10) O2 catechol (20) DMSO rt 62
9 Pd(OAc)2 (10) Cu(OAc)2 (10) O2 catechol (20) MeCN rt 65
10 Pd(OAc)2 (10) Cu(OAc)2 (10) O2 catechol (20) THF rt 39
11 Pd(TFA)2 (10) Cu(OAc)2 (10) O2 catechol (20) DMF rt 81
12 PdCl2 (10) Cu(OAc)2 (10) O2 catechol (20) DMF rt 57
13 Pd(TFA)2 (10) CuCl2 (10) O2 catechol (20) DMF rt 27
14 Pd(TFA)2 (10) Cu(OAc)2 (10) O2 catechol (20) + 4Å MS DMF rt 91 (89[c])
[a]

Other conditions: 1 (0.10 mmol), 2 (0.40 mmol), balloon (1 atm), solvent (0.5 mL), 24 h (PMP = para-methoxyphenyl).

[b]

1H NMR yields with Ph3SiMe (1.0 equiv) as the internal standard.

[c]

Isolated yield. (Detailed optimization is in the Supporting Information.)