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. Author manuscript; available in PMC: 2016 Jun 17.
Published in final edited form as: J Am Chem Soc. 2015 Jun 4;137(23):7290–7293. doi: 10.1021/jacs.5b04289

Table 1.

Optimization of the enantioselective relay Heck reaction of 2a.

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Entry Pd source Solvent yield of 3a (%)a er (3a)b δ:γc
1 Pd(MeCN)2(OTs)2 DMF 73 98:2 5.8
2 None DMF – – –
3 Pd(MeCN)2(OTs)2d DMF trace – –
4 Pd(MeCN)2(OTs)2e DMF trace – –
5 Pd(MeCN)2(OTs)2f DMF 65 98:2 5.2
6 Pd(MeCN)2(OTs)2 DMA 78 99:1 15
7 Pd(MeCN)2(OTs)2 1,4-dioxane 73 98:2 7.8
8 Pd(MeCN)2(OTs)2 THF 38 98:2 9.3

Conditions: 1a (0.75 mmol, 3.0 eq), 2a (0.25 mmol, 1.0 eq), [Pd] (0.01875 mmol, 7.5 mol%), ligand (0.0225 mmol, 9 mol%), solvent (3 mL), O2 (1 atm), rt, 24 h.

a

Reported yields are of isolated 3a as a >20:1 ratio of the E-alkene isomer.

b

Determined by SFC equipped with a chiral stationary phase.

c

Determined by NMR.

d

In the absence of 3Å MS.

e

In the absence of ligand.

f

Using air (1 atm). DMF = N,N-dimethylformamide; DMA = N,N-dimethylacetamide, THF = tetrahydrofuran.