Bromoform → (2S,4aS,6aR,7R,9R,10aS,10bR)-9-(Bromo)-2-(3-furanyl)-dodecahydro-6a,10b-dimethyl-4,10-dioxo-2H-naphtho[2,1-c]pyran-7-carboxylic acid methyl ester

A mixture of salvinorin B (8a) (0.15 g, 0.38 mmol), triphenylphosphine (0.21 g, 0.80 mmol), and bromoform (0.15 g, 0.45 mmol) in CH2Cl2 (30 mL) was stirred at room temperature overnight. TLC indicated that starting material was still present after 16 h, thus additional triphenylphosphine (0.11 g, 0.42 mmol) and bromoform (0.07 g, 0.21 mmol) were added and the mixture was stirred for an additional 3 h. The solvent was removed under reduced pressure affording a crude solid. The oil was purified by column chromatography (eluent: 30% EtOAc/n-hexanes) to afford 0.10 g (59%) of 36 as a white solid, mp 170-173° C. (EtOAc/n-hexanes); 1H NMR (CDCl3): δ 1.15 (3H, s); 1.48 (3H, s); 1.60 (3H, m); 1.81 (1H, dd, J=2.7, 9.9); 1.95 (1H, dd, J=13.2, 26.1); 2.1 (2H, m); 2.27 (1H, s); 2.47 (1H, dd, J=4.8, 13.2); 2.66 (1H, m); 2.80 (1H, dd, J=3.3, 13.2); 3.70 (3H, s); 3.89 (2H, d, J=2.4); 4.45 (1H, m); 5.55 (1H, dd, J=4.8, 11.7); 6.38 (1H, dd, J=0.9, 1.5); 7.4 (2H, m).

1. waitwas still present after 16 h
2. stirringthe mixture was stirred for an additional 3 h
3. customThe solvent was removed under reduced pressure
4. customaffording a crude solid
5. customThe oil was purified by column chromatography (eluent: 30% EtOAc/n-hexanes)

ORDレコード

ord-f9487c4143a64edc9e1870c4f003f434

出典データセット

uspto-grants-2010_06

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US07728001B2