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. Author manuscript; available in PMC: 2012 May 10.
Published in final edited form as: J Am Chem Soc. 2011 Apr 15;133(18):6902–6905. doi: 10.1021/ja200664x

Table 1.

Optimization of Reaction Conditions.a

graphic file with name nihms-289741-t0002.jpg

entry Pd source solvent temp (°C) yield (%)b ee (%)c
1 PdCl2 CH2Cl2 40 – –
2 Pd(MeCN)2Cl2 CH2Cl2 40 – –
3d Pd(MeCN)2Cl2, AgOTf CH2Cl2 40 69 17
4 Pd(OAc)2 CH2Cl2 40 65 92
5 Pd(OCOCF3)2 CH2Cl2 40 87 91
6 Pd(OCOCF3)2 ClCH2CH2Cl 60 99 93
7e Pd(OCOCF3)2 ClCH2CH2Cl 60 99 91
8f Pd(OCOCF3)2 ClCH2CH2Cl 60 99 93
9g Pd(OCOCF3)2 ClCH2CH2Cl 60 97 91
a

Conditions: Reactions were performed with phenylboronic acid (0.50 mmol), 3-methylcyclohexen-2-one (0.25 mmol), Pd(OCOCF3)2 (5 mol%), and ligand 4 (6 mol%) in solvent (1 mL) for 12 h, unless otherwise noted.

b

Isolated yield.

c

ee was determined by chiral HPLC, see Supporting Information.

d

12 mol% AgOTf.

e

Reaction performed in the presence of added H2O (2.5 mmol, 10 equiv).

f

Phenylboronic acid loading reduced to 1.1 equiv.

g

Multi gram scale-up reaction performed with 3-methylcyclohexen-2-one (2.42 g, 22.0 mmol), phenylboronic acid (44.0 mmol), H2O (5 equiv), Pd(OCOCF3)2 (5 mol%), and ligand 4 (6 mol%) in solvent (88 mL) for 12 h.