Stereochemistry of the Cyclization-Rearrangement of (+)-Copalyl Diphosphate to (−)-Abietadiene Catalyzed by Recombinant Abietadiene Synthase from Abies grandis

Syntheses and enzymatic cyclizations of 8α-hydroxy-17-nor copalyl diphosphate (8a), (15R)-[15-2H1] 8b, and (15R,17E)-[15-3H1,17-2H1] copalyl diphosphate ([2H,3H] 2) catalyzed by recombinant abietadiene synthase (rAS) gave 17-nor manoyl oxide (9a), (16E)-[16-2H1] 9b, and (15S,16R)-[16-2H1,16-3H1] abi...

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Published inOrganic letters Vol. 2; no. 5; pp. 573 - 576
Main Authors Ravn, Matthew M, Coates, Robert M, Flory, Janice E, Peters, Reuben J, Croteau, Rodney
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 09.03.2000
Amer Chemical Soc
Subjects
Catalysis
Chemistry
Chemistry, Organic
Diterpenes, Abietane
Isomerases - chemistry
Organophosphates - chemistry
Phenanthrenes - chemistry
Physical Sciences
Recombinant Proteins - chemistry
Science & Technology
Stereoisomerism
Trees - enzymology
ALCOHOLS
REDUCTIONS
CYCLASE
RESIN ACID BIOSYNTHESIS
CONVERSION
PYROPHOSPHATE
CONIFERS
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Summary:Syntheses and enzymatic cyclizations of 8α-hydroxy-17-nor copalyl diphosphate (8a), (15R)-[15-2H1] 8b, and (15R,17E)-[15-3H1,17-2H1] copalyl diphosphate ([2H,3H] 2) catalyzed by recombinant abietadiene synthase (rAS) gave 17-nor manoyl oxide (9a), (16E)-[16-2H1] 9b, and (15S,16R)-[16-2H1,16-3H1] abietadiene ([2H1,3H1] 4), respectively. These and other results indicate that conversion of CPP (2) to abietadiene (4) occurs by anti SN‘ cyclization to a sandaracopimar-15-en-8-yl carbocation intermediate (13 + , 13β-methyl) followed by hydrogen transfer and methyl migration suprafacially on the si face of the vinyl group.
Bibliography:Medline
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ISSN:1523-7060
1523-7052
DOI:10.1021/ol991230p