PMID- 20201526
OWN - NLM
STAT- MEDLINE
DCOM- 20100706
LR  - 20231213
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Linking)
VI  - 132
IP  - 12
DP  - 2010 Mar 31
TI  - Bisabolyl-derived sesquiterpenes from tobacco 5-epi-aristolochene 
      synthase-catalyzed cyclization of (2Z,6E)-farnesyl diphosphate.
PG  - 4281-9
LID - 10.1021/ja909886q [doi]
AB  - We report the structures and stereochemistry of seven bisabolyl-derived 
      sesquiterpenes arising from an unprecedented 1,6-cyclization (cisoid pathway) 
      efficiently catalyzed by tobacco 5-epi-aristolochene synthase (TEAS). The use of 
      (2Z,6E)-farnesyl diphosphate as an alternate substrate for recombinant TEAS 
      resulted in a robust enzymatic cyclization to an array of products derived 
      exclusively (>/=99.5%) from the cisoid pathway, whereas these same products 
      account for ca. 2.5% of the total hydrocarbons obtained using (2E,6E)-farnesyl 
      diphosphate. Chromatographic fractionations of extracts from preparative 
      incubations with the 2Z,6E substrate afforded, in addition to the acyclic allylic 
      alcohols (2Z,6E)-farnesol (6.7%) and nerolidol (3.6%), five cyclic sesquiterpene 
      hydrocarbons and two cyclic sesquiterpene alcohols: (+)-2-epi-prezizaene (44%), 
      (-)-alpha-cedrene (21.5%), (R)-(-)-beta-curcumene (15.5%), alpha-acoradiene 
      (3.9%), 4-epi-alpha-acoradiene (1.3%), and equal amounts of alpha-bisabolol 
      (1.8%) and epi-alpha-bisalolol (1.8%). The structures, stereochemistry, and 
      enantiopurities were established by comprehensive spectroscopic analyses, optical 
      rotations, chemical correlations with known sesquiterpenes, comparisons with 
      literature data, and GC analyses. The major product, (+)-2-epi-prezizaene, is 
      structurally related to the naturally occurring tricyclic alcohol, jinkohol 
      (2-epi-prezizaan-7beta-ol). Cisoid cyclization pathways are proposed by which all 
      five sesquiterpene hydrocarbons are derived from a common 
      (7R)-beta-bisabolyl(+)/pyrophosphate(-) ion pair intermediate. The implications 
      of the "cisoid" catalytic activity of TEAS are discussed.
FAU - Faraldos, Juan A
AU  - Faraldos JA
AD  - Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South 
      Mathews Avenue, Urbana, Illinois 61801, USA.
FAU - O'Maille, Paul E
AU  - O'Maille PE
FAU - Dellas, Nikki
AU  - Dellas N
FAU - Noel, Joseph P
AU  - Noel JP
FAU - Coates, Robert M
AU  - Coates RM
LA  - eng
GR  - R01 GM013956/GM/NIGMS NIH HHS/United States
GR  - GM 13956/GM/NIGMS NIH HHS/United States
GR  - Howard Hughes Medical Institute/United States
PT  - Journal Article
PT  - Research Support, N.I.H., Extramural
PT  - Research Support, Non-U.S. Gov't
PT  - Research Support, U.S. Gov't, Non-P.H.S.
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
RN  - 0 (5-epi-aristolochene)
RN  - 0 (Monocyclic Sesquiterpenes)
RN  - 0 (Polyisoprenyl Phosphates)
RN  - 0 (Recombinant Proteins)
RN  - 0 (Sesquiterpenes)
RN  - 24WE03BX2T (bisabolol)
RN  - 79W6B01D07 (farnesyl pyrophosphate)
SB  - IM
MH  - Catalysis
MH  - Cyclization
MH  - Molecular Structure
MH  - Monocyclic Sesquiterpenes
MH  - Polyisoprenyl Phosphates/*chemistry
MH  - Recombinant Proteins/genetics
MH  - Sesquiterpenes/*chemistry/classification
MH  - Nicotiana/*enzymology
EDAT- 2010/03/06 06:00
MHDA- 2010/07/07 06:00
CRDT- 2010/03/06 06:00
PHST- 2010/03/06 06:00 [entrez]
PHST- 2010/03/06 06:00 [pubmed]
PHST- 2010/07/07 06:00 [medline]
AID - 10.1021/ja909886q [doi]
PST - ppublish
SO  - J Am Chem Soc. 2010 Mar 31;132(12):4281-9. doi: 10.1021/ja909886q.