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Title: Biosynthesis of monoterpenes: Stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes

Abstract

The conversion of geranyl pyrophosphate to (+)-bornyl pyrophosphate and (+)-camphene is considered to proceed by the initial isomerization of the substrate to (-)-(3R)-linalyl pyrophosphate and the subsequent cyclization of this bound intermediate. In the case of (-)-bornyl pyrophosphate and (-)-camphene, isomerization of the substrate to the (+)-(3S)-linalyl intermediate precedes cyclization. The geranyl and linalyl precursors were shown to be mutually competitive substrates (inhibitors) of the relevant cyclization enzymes isolated from Salvia officinalis (sage) and Tanacetum vulgare (tansy) by the mixed substrate analysis method, demonstrating that isomerization and cyclization take place at the same active site. Incubation of partially purified enzyme preparations with (3R)-(1Z-3H)linalyl pyrophosphate plus (1-14C)geranyl pyrophosphate gave rise to double-labeled (+)-bornyl pyrophosphate and (+)-camphene, whereas incubation of enzyme preparations catalyzing the antipodal cyclizations with (3S)-(1Z-3H)-linalyl pyrophosphate plus (1-14C)geranyl pyrophosphate yielded double-labeled (-)-bornyl pyrophosphate and (-)-camphene. Each product was then transformed to the corresponding (+)- or (-)-camphor without change in the 3H:14C isotope ratio, and the location of the tritium label was deduced in each case by stereoselective, base-catalyzed exchange of the exo-alpha-hydrogen of the derived ketone. The finding that the 1Z-3H of the linalyl precursor was positioned at the endo-alpha-hydrogen of the corresponding camphor in all cases, coupled tomore » the previously demonstrated retention of configuration at C1 of the geranyl substrate in these transformations, confirmed the syn-isomerization of geranyl pyrophosphate to linalyl pyrophosphate and the cyclization of the latter via the anti,endo- conformer.« less

Authors:
; ; ;  [1]
  1. Washington State Univ., Pullman (USA)
Publication Date:
OSTI Identifier:
7137989
Resource Type:
Journal Article
Journal Name:
Archives of Biochemistry and Biophysics; (USA)
Additional Journal Information:
Journal Volume: 277:2; Journal ID: ISSN 0003-9861
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; PYROPHOSPHATES; ISOMERIZATION; TERPENES; BIOSYNTHESIS; CAMPHENE; CARBON 14 COMPOUNDS; DOUBLE LABELLING; ISOTOPE DILUTION; ISOTOPE RATIO; PRECURSOR; STEREOCHEMISTRY; TRITIUM COMPOUNDS; ALKENES; CHEMICAL REACTIONS; CYCLOALKENES; HYDROCARBONS; HYDROGEN COMPOUNDS; ISOTOPE APPLICATIONS; LABELLED COMPOUNDS; LABELLING; ORGANIC COMPOUNDS; OXYGEN COMPOUNDS; PHOSPHORUS COMPOUNDS; SYNTHESIS; TRACER TECHNIQUES; 550201* - Biochemistry- Tracer Techniques

Citation Formats

Croteau, R, Gershenzon, J, Wheeler, C J, and Satterwhite, D M. Biosynthesis of monoterpenes: Stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes. United States: N. p., 1990. Web. doi:10.1016/0003-9861(90)90593-N.
Croteau, R, Gershenzon, J, Wheeler, C J, & Satterwhite, D M. Biosynthesis of monoterpenes: Stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes. United States. https://doi.org/10.1016/0003-9861(90)90593-N
Croteau, R, Gershenzon, J, Wheeler, C J, and Satterwhite, D M. 1990. "Biosynthesis of monoterpenes: Stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes". United States. https://doi.org/10.1016/0003-9861(90)90593-N.
@article{osti_7137989,
title = {Biosynthesis of monoterpenes: Stereochemistry of the coupled isomerization and cyclization of geranyl pyrophosphate to camphane and isocamphane monoterpenes},
author = {Croteau, R and Gershenzon, J and Wheeler, C J and Satterwhite, D M},
abstractNote = {The conversion of geranyl pyrophosphate to (+)-bornyl pyrophosphate and (+)-camphene is considered to proceed by the initial isomerization of the substrate to (-)-(3R)-linalyl pyrophosphate and the subsequent cyclization of this bound intermediate. In the case of (-)-bornyl pyrophosphate and (-)-camphene, isomerization of the substrate to the (+)-(3S)-linalyl intermediate precedes cyclization. The geranyl and linalyl precursors were shown to be mutually competitive substrates (inhibitors) of the relevant cyclization enzymes isolated from Salvia officinalis (sage) and Tanacetum vulgare (tansy) by the mixed substrate analysis method, demonstrating that isomerization and cyclization take place at the same active site. Incubation of partially purified enzyme preparations with (3R)-(1Z-3H)linalyl pyrophosphate plus (1-14C)geranyl pyrophosphate gave rise to double-labeled (+)-bornyl pyrophosphate and (+)-camphene, whereas incubation of enzyme preparations catalyzing the antipodal cyclizations with (3S)-(1Z-3H)-linalyl pyrophosphate plus (1-14C)geranyl pyrophosphate yielded double-labeled (-)-bornyl pyrophosphate and (-)-camphene. Each product was then transformed to the corresponding (+)- or (-)-camphor without change in the 3H:14C isotope ratio, and the location of the tritium label was deduced in each case by stereoselective, base-catalyzed exchange of the exo-alpha-hydrogen of the derived ketone. The finding that the 1Z-3H of the linalyl precursor was positioned at the endo-alpha-hydrogen of the corresponding camphor in all cases, coupled to the previously demonstrated retention of configuration at C1 of the geranyl substrate in these transformations, confirmed the syn-isomerization of geranyl pyrophosphate to linalyl pyrophosphate and the cyclization of the latter via the anti,endo- conformer.},
doi = {10.1016/0003-9861(90)90593-N},
url = {https://www.osti.gov/biblio/7137989}, journal = {Archives of Biochemistry and Biophysics; (USA)},
issn = {0003-9861},
number = ,
volume = 277:2,
place = {United States},
year = {Thu Mar 01 00:00:00 EST 1990},
month = {Thu Mar 01 00:00:00 EST 1990}
}