Table 1.

Asymmetric Epoxidation of Non-conjugated cis-Olefins^a

entry	substrate	product	ketone	temp (°C)	time (h)	yield (%)b	ee (%)
1c			2d	0	8	52	64d,8
2			2d	−10	8	71	79e,f,12
3			2d	−10	4	89	82e,13
4			2d	−10	8	75	91d,f,11h
5			2d	−10	8	85	86g,14
6			2a	−10	8	79	61d,h
7i,j,k			2a	−10	12	73	86d
8i,j,k			2a	−10	12	71	85d,h
9			2a	−10	12	80	32l
10i,j			2a	−10	12	76	92d
11i,j			2a	0	12	39	51d
12			2a	0	8	87	59d,5b,15

^aFor ketone 2d unless otherwise stated, all reactions were carried out with olefin (1.0 equiv), catalyst (0.25 equiv), Oxone (1.6 equiv), and K₂CO₃ (6.7 equiv) in DME/DMM (3:1, v/v) and buffer (0.1 M K₂CO₃-AcOH in 4 × 10⁻⁴ M aq EDTA, pH 9.3) (1.5:1, v/v). For ketone 2a unless otherwise stated, all reactions were carried out with olefin (1.0 equiv), catalyst (0.25 equiv), Oxone (1.6 equiv), and K₂CO₃ (3.8 equiv) in DME/DMM/n-BuOH (3:1:2, v/v/v) and buffer (0.1 M K₂CO₃-AcOH in 4 × 10⁻⁴ M aq EDTA, pH 8.0) (4:1, v/v). In both cases Oxone and K₂CO₃ were added separately and simultaneously over the time and temperature specified.

^bIsolated yield.

^cDME was used as solvent.

^dThe ee was determined by chiral GC (Chiraldex B-DM column).

^eThe ee was determined by chiral GC (Chiraldex B-DM column) of the methyl ether derivative.

^fAbsolute stereochemistry was determined by comparing the optical rotation of the epoxide or its derivate with the reported one.

^gRelative stereochemistry indicated. The ee was determined by chiral HPLC (Chiralpak AD column) of the benzoate derivative.

^hAbsolute stereochemistry was determined by converting a compound of known configuration to the epoxide of interest and comparing the optical rotation and chiral GC elution order.

ⁱ0.30 equiv catalyst was used.

^j2.9 equiv Oxone and 6.9 equiv K₂CO₃ were used.

^kDME/DMM (3:1, v/v) was used as solvent; the solvent/buffer ratio was 1.5:1 (v/v).

^lThe ee was determined by chiral HPLC (Chiralcel OD column).