Dimethyldioxirane → 2-Benzyloxymethyl-1,5-dioxaspiro[3.2]hexane

HRID 898689Notes

Reaction equation

[CH2:1]([O:8][CH2:9][CH:10]1[O:13][C:12](=[CH2:14])[CH2:11]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC1(C)O[O:17]1>C(Cl)Cl>[CH2:1]([O:8][CH2:9][CH:10]1[CH2:11][C:12]2([CH2:14][O:17]2)[O:13]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

Conditions

Temperature: -78 °C

Procedure

A solution of 4-benzyloxymethyl-2-methyleneoxetane (0.025 g, 0.13 mmol) in CH2Cl2 under N2 was cooled to −78° C. Then, dimethyldioxirane (0.5 M, 0.52 mL, 0.26 mmol) was added dropwise, and the reaction was stirred at −78° C. for 1 h. The solvent was then evaporated to give 2-benzyloxymethyl-1.5-dioxaspiro[3.2]hexane, which was dissolved in dry THF (2 mL). The solution was stirred under N2 and cooled to 0° C. A solution of 1H-tetrazole (0.01 g, 0.14 mmol) in dry THF (2.0 mL) was added. The reaction mixture was stirred at 0° C. for 3 h and was then warmed to room temperature, followed by removal of the solvent in vacuo. The resultant oil was purified by preparatory TLC on silica gel (CH2Cl2/MeOH 96:4). 4-Benzyloxymethyl-2-hydroxymethyl-2-(tetrazol-2-yl)oxetane was isolated as a clear oil was (32 mg, 88% over 2 steps). 1H NMR (400 MHz, CDCl3) δ 8.61 (s, 1H), 7.34 (m, 5H), 5.23 (m, 1H), 4.69 (d, J=11.9 Hz, 1H), 4.63 (d, J=11.9 Hz, 1H), 4.40 (app d, J=12.6 Hz, 1H), 4.17 (dd, J=12.2, 8.7 Hz, 1H), 3.83 (dd, J=11.7, 2.2 Hz, 1H), 3.68 (dd, J=11.7, 2.8 Hz, 1H), 3.60 (dd, J=12.3, 7.2 Hz, 1H), 3.40 (dd, J=12.3, 7.6 Hz, 1H), 3.24 (app d, J=5.4 Hz, 1H); 3C NMR (100 MHz, CDCl3) δ 153.4, 137.6, 129.1, 128.6, 128.4, 97.8, 76.8, 74.2, 71.0, 65.4, 30.2; MS (EI) m/z 149, 107, 91 (100), 77, 65.

Workup

customThe solvent was then evaporated

Sources & evidence

ORD record: ord-ed31e936b6284cd6b2414f97c81a9d2d
Source dataset: uspto-grants-2008_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07351827B2

Reaction notes

Loading…