Triphenylphosphine → 2-tert-Butoxycarbonylamino-2-(2-oxo-ethyl)-6-(4,4,5,5-tetramethyl-[1,3,2]-dioxaborolan-2-yl)-hexanoic acid ethyl ester

HRID 579491노트

반응식

HRID 579491 반응식
[CH2:1]([O:3][C:4](=[O:30])[C:5]([CH2:27][CH:28]=C)([NH:19][C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[CH2:6][CH2:7][CH2:8][CH2:9][B:10]1[O:14][C:13]([CH3:16])([CH3:15])[C:12]([CH3:18])([CH3:17])[O:11]1)[CH3:2].[O:31]=[O+][O-].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl>[CH2:1]([O:3][C:4](=[O:30])[C:5]([NH:19][C:20]([O:22][C:23]([CH3:25])([CH3:26])[CH3:24])=[O:21])([CH2:27][CH:28]=[O:31])[CH2:6][CH2:7][CH2:8][CH2:9][B:10]1[O:11][C:12]([CH3:17])([CH3:18])[C:13]([CH3:15])([CH3:16])[O:14]1)[CH3:2]

참가 물질

5

반응물 3

HCID 11776TriphenylphosphineHCID 24823Ozone2회HCID 66833330Ethyl-2-allyl-2-(tert-butoxycarbonylamino)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexanoate

생성물 1

HCID 866637142-tert-Butoxycarbonylamino-2-(2-oxo-ethyl)-6-(4,4,5,5-tetramethyl-[1,3,2]-dioxaborolan-2-yl)-hexanoic acid ethyl ester수율 93%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

A solution of Ethyl-2-allyl-2-(tert-butoxycarbonylamino)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)hexanoate (650 mg, 1.53 mmol) in dichloromethane (30 mL,) was cooled to −78° C. and treated with ozone until a pale blue-gray color appeared. After TLC indicated the absence of starting material, the ozone inlet tube was replaced with nitrogen and nitrogen was bubbled through the solution for 20 min to remove any excess ozone. Triphenylphosphine (1.20 g, 4.59 mmol, 3 equiv) was added in one portion, the cooling bath was removed and the mixture was stirred for 4 h. The solution was concentrated and purified by MPLC (0-40% ethyl acetate in heptane) gave the title compound as a colorless oil (608 mg, 93%). Rf 0.25 (30% ethyl acetate in heptane); 1H NMR (CDCl3, 300 MHz): δ 9.64 (s, CHO, 1H), 5.60 (br, s, NH, 1H), 4.19 (q, J=7.5 Hz, 2H), 3.56 (d, J=17 Hz, 1H), 2.93 (d, J=17.5 Hz, 1H), 2.20 (m, 1H), 1.62 (m, 1H), 1.38 (s, 9H), 1.28-1.43 (m, 4H), 1.23 (t, J=7 Hz, 3H), 1.21 (s, 12H) and 0.72 (t, J=7.5 Hz, 2H).

후처리

  1. customwas bubbled through the solution for 20 min
  2. customto remove any excess ozone
  3. customthe cooling bath was removed
  4. concentrationThe solution was concentrated
  5. custompurified by MPLC (0-40% ethyl acetate in heptane)

출처 및 근거

ORD 기록
ord-b5288f0940934535aae1006d802ef89d
출처 데이터셋
uspto-grants-2015_05
특허 번호
US09040703B2

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