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. Author manuscript; available in PMC: 2015 Sep 8.
Published in final edited form as: Chemistry. 2014 Jul 30;20(37):11726–11739. doi: 10.1002/chem.201402353

Table 4.

Optimization of Pd-catalyzed Suzuki-Miyaura cross-coupling of 2-B(pin)-substituted allylic acetate 1a.

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Entry Pd/ligand[a] Base[b] Solvent[c] Conc.(M)[d] Time (h) yield (%)[e]
1 Pd(OAc)2/PPh3 (15 mol %, 1:2) Cs2CO3 THF 0.022 24 90[f]
2 Pd(OAc)2/PPh3 (10 mol %, 1:2) Cs2CO3 THF 0.022 48 62
3 Pd(OAc)2/P(o-Tol)3 (10 mol %, 1:2) Cs2CO3 THF 0.022 48 20
4 Pd(OAc)2/DPPP (10 mol %, 1:1) Cs2CO3 THF 0.022 48 32
5 Pd(OAc)2/DPPE (10 mol %, 1:1) Cs2CO3 THF 0.022 48 27
6 Pd(OAc)2/DPPF (10 mol %, 1:1) Cs2CO3 THF 0.022 48 62
7 Pd(OAc)2/P(t-Bu)3 (10 mol %, 1:1) Cs2CO3 THF 0.022 48 80
8 Pd(PPh3)4 (10 mol %) Cs2CO3 THF 0.022 36 87
9 PdCl2(PPh3)2/PPh3 (10 mol %, 1:1) Cs2CO3 THF 0.08 24 71
10 PdCl2(PPh3)2/PPh3 (10 mol %, 1:1) Cs2CO3 Dioxane 0.08 18 61
11 PdCl2(PPh3)2/PPh3 (10 mol %, 1:1) CsF Dioxane 0.08 18 25
12 PdCl2(PPh3)2/PPh3 (10 mol %, 1:1) K3PO4 toluene 0.08 24 52
13 Pd(OAc)2/PPh3 (10 mol %, 1:3) Cs2CO3 toluene 0.17 4 96[f]
14 Pd(OAc)2/PPh3 (5 mol %, 1:3) Cs2CO3 toluene 0.17 18 95[f],[g]
15 PdCl2(PPh3)2/PPh3 (5 mol %, 1:1) Cs2CO3 toluene 0.17 18 93[f],[g]
16 Pd(PPh3)4 (10 mol %) Cs2CO3 toluene 0.17 18 96[f],[g]
[a]

mol % of Pd and molar ratio of Pd to phosphine provided in parenthesis.

[b]

3 equiv of base and iodobenzene used unless otherwise noted.

[c]

10:1 ratio of solvent to H2O.

[d]

Ratio of 1a (mmol)/solvent (mL).

[e]

Yield determined by 1H NMR integration of the crude reaction mixture using 1,4-dimethoxybenzene as the internal standard.

[f]

Yield of isolated and purified products.

[g]

2 equiv of Cs2CO3 and iodobenzene used.