Dimethyldioxirane → Epothilone B

HRID 2354109Notes

Reaction equation

[CH3:1][C@@H:2]1[C@H:19]([OH:20])[C@@H:18]([CH3:21])[C:16](=[O:17])[C:15]([CH3:23])([CH3:22])[C@@H:14]([OH:24])[CH2:13][C:11](=[O:12])[O:10][C@H:9](/[C:25](/[CH3:33])=[CH:26]/[C:27]2[N:31]=[C:30]([CH3:32])[S:29][CH:28]=2)[CH2:8][CH:7]=[C:6]([CH3:34])[CH2:5][CH2:4][CH2:3]1.CC1(C)O[O:37]1>>[CH3:1][C@@H:2]1[C@H:19]([OH:20])[C@@H:18]([CH3:21])[C:16](=[O:17])[C:15]([CH3:22])([CH3:23])[C@@H:14]([OH:24])[CH2:13][C:11](=[O:12])[O:10][C@H:9](/[C:25](/[CH3:33])=[CH:26]/[C:27]2[N:31]=[C:30]([CH3:32])[S:29][CH:28]=2)[CH2:8][C@@H:7]2[O:37][C@:6]2([CH3:34])[CH2:5][CH2:4][CH2:3]1

Participants

Reactant 2

HCID 115197Dimethyldioxirane

HCID 447865Epothilone D

Product 1

HCID 448013Epothilone B

Conditions

Temperature: -50 °C

Procedure

To a solution of desoxyepothilone B (0.0022 g, 0.0041 mmol) in CH2CI2 (0.25 mL) at −50° C. was added dimethyldioxirane (0.1 mL, 0.0095 mmol) dropwise. The resulting solution was stirred at −50° C. for 1 h. The dimethyldioxirane and solvent were removed by a stream of N2. The residue was purified by flash column chromatography (hexanes/ethyl acetate, 1:1) gave 0.0015 g (70%) of epothiolone B (2) as a pale yellow oil which was identical with an authentic sample in 1H NMR, IR, mass spectrum, and [α]D.

Workup

customThe dimethyldioxirane and solvent were removed by a stream of N2
customThe residue was purified by flash column chromatography (hexanes/ethyl acetate, 1:1)

Sources & evidence

ORD record: ord-4d845f1ef0534ae6952736631e649807
Source dataset: uspto-grants-2010_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07750164B2

Reaction notes

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