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. Author manuscript; available in PMC: 2012 Dec 30.
Published in final edited form as: Tetrahedron. 2011 Dec 30;67(52):10234–10248. doi: 10.1016/j.tet.2011.10.031

Table 2.

Scope of the Pd-catalyzed enantioselective alkylation of cyclic vinylogous esters.a

graphic file with name nihms-332928-f0006.jpg
entry substrate 6 R product 7 yieldb(%) eec(%)
1 6a –CH3 7a 91 88
2 6b –CH2CH3 7b 89 92
3 6c –CH2Ph 7c 98 86
4 6d –CH2C≡CH 7d 88 89
5 6e –CH2CH2CH=CH2 7e 95 87
6 6f graphic file with name nihms-332928-t0007.jpg 7f 90 90
7 6g graphic file with name nihms-332928-t0008.jpg 7g 99 86
8 6h –CH2CH2CN 7h 96 87
9 6i graphic file with name nihms-332928-t0009.jpg 7i 97 85
10 6j graphic file with name nihms-332928-t0010.jpg 7j 98 83
11 6k graphic file with name nihms-332928-t0011.jpg 7k 90 80
12 61 –F 71 94 91
13 6m –CH2OTBDPSd 7m 66 58
14 6n graphic file with name nihms-332928-t0012.jpg 7n 75 57
a

Conditions: β-ketoester 6 (1.0 equiv), Pd2(pmdba)3 (2.5 mol %), (S)-t-Bu-PHOX (L1, 6.25 mol %) in PhCH3 (0.1 M) at 30 °C; pmdba = 4,4’-methoxydibenzylideneacetone.

b

Isolated yield.

c

Determined by chiral HPLC or SFC.

d

TBDPS = tert-butyldiphenylsilyl, Ts = 4-toluenesulfonyl.