Formic Acid → (S)-Citronellene

Temperature

20 °C

In a Schlenk's tube, (R)-(+)-3-diphenylphosphino-3'-methoxy-4,4'-biphenanthryl prepared in Example 1 (6.24 mg, 0.011 mmol) and tris(dibenzylideneacetone)(chloroform)dipalladium (0) (2.6 mg, 0.0025 mmol) were charged, and dioxane was added under a nitrogen atmosphere. To the mixture cooled on an ice bath, 1,8-bis(dimethylamino)naphthalene (128.6 mg, 0.60 mmol) and formic acid (52.5 mg, 1.14 mmol) were added in this order. At the same temperature, geranylmethyl carbonate (104.5 mg, 0.49 mmol) was added, and the mixture was stirred at 20° C. for 17 hours. The reaction mixture was diluted with pentane and washed with water, and the organic layer was dried over anhydrous magnesium sulfate and filtrated through a mass of silica gel. From the filtrate, the solvent was evaporated off under reduced pressure to obtain (S)-3,7-dimethyl-1,6-octadiene as a colorless oil (68.0 mg). Yield, >99%. Rotatory power: :[α]D20 =+8.1 (C=1.6, CHCl3). 1 H-NMR (CDCl3): δ(ppm)=0.98 (d, J=7.0 Hz, 3H), 1.27-1.36 (m, 2H), 1.60 (s, 3H), 1.67 (s, 3H), 1.96 (q, J=7.0 Hz, 2H), 2.12 (heptet, J=7 Hz, 1H), 4.88-4.99 (m, 2H), 5.05-5.15 (m, 1H), 5.70 (ddd, J=17.1, 10.1 and 7.0 Hz, 1H).

1. temperatureTo the mixture cooled on an ice bath
2. washwashed with water
3. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
4. filtrationfiltrated through a mass of silica gel
5. customFrom the filtrate, the solvent was evaporated off under reduced pressure

ORD record

ord-a593567663414f2ea842f89088d38899

Source dataset

uspto-grants-1996_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05523437