Neryl phosphates

Allylic phosphates are used for carbonylation in the presence of amines under pressure. Carbonylation of diethyl neryl phosphate (389) affords ethyl homonerate (390), maintaining the geometric integrity of the double bond[244]. The carbonylation of allyl phosphate in the presence of the imine 392 affords the /3-lactam 393. The reaction may be explained by the formation of the ketene 391 from the acyl phosphate, and its stereoselective (2 + 2] cycloaddition to the imine 392 to give the /3-lactam 393(247],... 

The cyclization of polyolefin terpenes occurs readily once they have been converted into terminal epoxides. The tetracyclic diterpenes 3a- and 3/S-kaurene have been prepared enzymically from chemically synthesized (/ ,5)-14,15-oxidogeranylgeranyl pyrophosphate (42), providing another example of this cyclization. Trimethyl-aluminium can promote the non-enzymic cyclization of the diethyl ester of neryl phosphate (43), presumably a carbonium ion, to 4-t-butyI-l-methylcyclohexene. ... 

Enzymes in cell-free systems from carrot Daucus carota, Apiaceae) and peppermint Mentha piperita Lamiaceae) catalyze the reversible formation of nerol and neryl phosphate from geraniol and geranyl phosphate, respectively. Geranyl phosphate appears to have been isomerized directly to the neryl derivative without the intervention of an aldehyde intermediate. The presence of a flavin, thiol, and light was required for the reaction (Croteau, 1984). 

Neryl diethyl phosphate, 471 Nickel(II) acetylacetonate, 42, 84 Nickel carbonyl, 515 Nickel chloride, 291 Nickel peroxide, 357-358 Nitrene, 250 Nitrile oxides, 464,465 Nitrules, 166, 228, 256, 409,415, 416, 504... 

In the next step, ohvetolic acid is condensed with geranyl diphosphate in the presence of a particular prenyltransferase. Olivetol itself is not active as a prenyl-acceptor. [128] Tracer experiments with C-labeUed glucose show that in hemp the terpene part of cannabinoids is constructed according to the newly-discovered deoxyxylulose phosphate pathway (the Rohmer route). Since can-nabinerolic acid is found as a second component, it appears likely that also neryl diphosphate is transformed by the same enzyme. 

Hexyl phosphate Hostaphat HI 3913-02-8 Butyloctanol ISOFOL 12 Jarcol 1-12 3913-71-1 2-Decenal 3913-81-3 trans-2-Decenal 3915-83-1 Neryl isovalerate 3918-73-8... 

M. are biosynthesized from geranyl pyrophosphate (see Terpenes) via its isomer neryl pyrophosphate (Fig.). Aliphatic M. arise by hydrolysis of the phosphate bond, or the elimination of pyrophosphate (synthesis of 3,7-dimethyloctane type). Cyclic M. usually arise by nucleophilic substitution at Cl of the neryl pyrophosphate with loss of pyrophosphate. Iridoid compounds arise from the reductive cyclization of neryl pyrophosphate. 

The formation of monoterpene hydrocarbons from geranyl and neryl diphenyl phosphates, J. Chem. Soc. 264 (1969). 

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