Dichloromethane → (1S,5R,7S,8S,9S)-7,9-Dihydroxy-4,9-dimethoxy-8-methyl-3,5-bis(3-methylbut-2-en-1-yl)-8-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-3-en-2-one

HRID 633651노트

반응식

C(Cl)Cl.[CH3:4][O:5][C:6]1[C@@:7]2([CH2:31][CH:32]=[C:33]([CH3:35])[CH3:34])[CH2:13][CH:11]3[O:12][C@@:8]2([O:29][CH3:30])[C@H:9]([C:21](=[O:28])[C:22]=1[CH2:23][CH:24]=[C:25]([CH3:27])[CH3:26])[C@:10]3([CH3:20])[CH2:14][CH2:15][CH:16]=[C:17]([CH3:19])[CH3:18].BrB(C)C.CCCCCC.CC[O:48]C(C)=O>>[OH:12][C@@H:11]1[C@@:10]([CH3:20])([CH2:14][CH2:15][CH:16]=[C:17]([CH3:18])[CH3:19])[C@@H:9]2[C@:8]([OH:48])([O:29][CH3:30])[C@@:7]([CH2:31][CH:32]=[C:33]([CH3:34])[CH3:35])([C:6]([O:5][CH3:4])=[C:22]([CH2:23][CH:24]=[C:25]([CH3:26])[CH3:27])[C:21]2=[O:28])[CH2:13]1

참가 물질

반응물 5

HCID 6344Dichloromethane2회

HCID 8058Hexane

HCID 8857Ethyl Acetate

HCID 123224Dimethylboronbromide

HCID 86718443(3S,3aS,7R,7aS)-6,7a-Dimethoxy-3-methyl-5,7-bis(3-methylbut-2-en-1-yl)-3-(4-methylpent-3-en-1-yl)-3,3a,7,7a-tetrahydro-2,7-methanobenzofuran-4(2H)-one

생성물 1

HCID 86718442(1S,5R,7S,8S,9S)-7,9-Dihydroxy-4,9-dimethoxy-8-methyl-3,5-bis(3-methylbut-2-en-1-yl)-8-(4-methylpent-3-en-1-yl)bicyclo[3.3.1]non-3-en-2-one수율 88%

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온도: -78 °C

실험 절차

A DCM (2 mL) solution of 15 (29 mg, 6.6 μmol, 1 equiv.) was cooled to −78° C. in a 10-mL teardrop-shaped flask, and a DCM solution of bromodimethylborane (2.65 M, 0.25 mL, 0.66 mmol, 10 equiv.) was added dropwise. After stirring the bright yellow solution at −78° C. for 10 min, it was quenched sequentially at −78° C. with 1.25 mL NEt3 and saturated aqueous NaHCO3. The mixture was warmed to room temperature and extracted thrice with EtOAc. The organic extracts were combined, washed with brine, dried over Na2SO4, filtered, and concentrated in vacuo to yield a yellow residue. Flash column chromatography (30 mL SiO2, 9:1 hexane:EtOAc) afforded 26.7 mg (58 μmol, 88% yield) of 17 as a yellow oil. TLC Rf 0.38 (7:3 hexane:EtOAc). 1H NMR (600 MHz; C6D6): δ 5.55 (dq, J=11.5, 1.3 Hz, 1H), 5.35 (t, J=7.3 Hz, 1H), 5.28 (t, J=6.6 Hz, 1H), 3.71 (s, 1H), 3.67 (dd, J=11.8, 5.3 Hz, 1H), 3.53 (s, 3H), 3.34 (dd, J=15.2, 6.4 Hz, 1H), 3.16 (m, 1H), 3.14 (s, 1H), 3.06 (s, 3H), 2.92 (dd, J=14.1, 11.5 Hz, 1H), 2.86 (tdd, J=12.8, 7.7, 5.0 Hz, 1H), 2.26 (d, J=14.1 Hz, 1H), 2.08 (tt, J=12.5, 6.1 Hz, 1H), 2.00 (dd, J=12.8, 12.0 Hz, 1H), 1.84 (s, 3H), 1.72 (s, 3H), 1.72-1.68 (m, 1H), 1.62 (s, 6H), 1.60-1.58 (m, 1H), 1.56 (s, 3H), 1.42 (s, 3H), 1.27 (td, J=12.7, 4.4 Hz, 1H), 1.12 (s, 3H). 13C NMR (126 MHz; C6D6): δ 197.3, 171.2, 136.5, 131.8, 131.1, 125.8, 124.5, 123.36, 123.23, 100.2, 73.4, 61.8, 57.5, 52.4, 48.2, 40.9, 39.7, 37.5, 30.8, 26.0, 25.76, 25.72, 23.7, 22.2, 18.01, 17.90, 17.7, 17.3. FTIR (thin film) νmax: 3464 (br), 2969, 2928, 2859, 1665, 1615, 1450, 1376, 1329, 1235, 1087, 1040, 986, 928, 907, 858, 737 cm-1. HRMS-ESI (m/z): [M+H]+ calculated for C28H44O5, 461.3262. found, 461.3254.

후처리

customit was quenched sequentially at −78° C. with 1.25 mL NEt3 and saturated aqueous NaHCO3
temperatureThe mixture was warmed to room temperature
extractionextracted thrice with EtOAc
washwashed with brine
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated in vacuo
customto yield a yellow residue

출처 및 근거

ORD 기록: ord-d6e653984ff944bb909408af34876469
출처 데이터셋: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
특허 번호: US09321713B2

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