Biosynthesis of Lycosantalonol, a cis-Prenyl Derived Diterpenoid Zi, Jiachen Matsuba, Yuki Hong, Young Jackson, Alana Tantillo, Dean Pichersky, Eran Peters, Reuben
dc.contributor.department Biochemistry, Biophysics and Molecular Biology 2020-04-02T15:17:08.000 2020-06-29T23:47:18Z 2020-06-29T23:47:18Z Wed Jan 01 00:00:00 UTC 2014 2014-12-12 2014-01-01
dc.description.abstract <p>Terpenoid natural products are generally derived from isoprenyl diphosphate precursors with trans double-bond configuration, and no diterpenoid derived from the cisoid precursor (<em>Z</em>,<em>Z</em>,<em>Z</em>)-nerylneryl diphosphate (<strong>1</strong>) has yet been identified. Here further investigation of a terpenoid biosynthetic gene cluster from tomato is reported, which resulted in identification of a biosynthetic pathway from <strong>1</strong>, in a pathway featuring a number of interesting transformations. Compound <strong>1</strong> is first cyclized to a tricyclene core ring structure analogous to that found in α-santalene, with the resulting diterpene termed here lycosantalene (<strong>2</strong>). Quantum chemical calculations indicate a role for the diphosphate anion coproduct in this cyclization reaction. Subsequently, the internal cis double bond of the neryl side chain in <strong>2</strong> is then further transformed to an α-hydroxy ketone moiety via an epoxide intermediate (<strong>3</strong>). Oxygen labeling studies indicate <strong>3</strong> undergoes oxidative conversion to lycosantalonol (<strong>4</strong>). Thus, in addition to elucidating the cisoid origins of <strong>4</strong>, this work has further provided mechanistic insight into the interesting transformations required for its production.</p>
dc.description.comments <p>Reprinted (adapted) with permission from <em>Journal of the American Chemical Society</em> 136 (2014): 16951, doi:<a href="" target="_blank">10.1021/ja508477e</a>. Copyright 2014 American Chemical Society.</p>
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dc.identifier archive/
dc.identifier.articleid 1012
dc.identifier.contextkey 6459466
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath bbmb_ag_pubs/6
dc.language.iso en
dc.source.bitstream archive/|||Sat Jan 15 01:06:15 UTC 2022
dc.source.bitstream archive/|||Sat Jan 15 01:06:17 UTC 2022
dc.source.uri 10.1021/ja508477e
dc.subject.disciplines Biochemistry, Biophysics, and Structural Biology
dc.subject.disciplines Genetics and Genomics
dc.subject.disciplines Natural Products Chemistry and Pharmacognosy
dc.subject.keywords diphosphate
dc.subject.keywords terpenoid
dc.subject.keywords cisoid
dc.title Biosynthesis of Lycosantalonol, a cis-Prenyl Derived Diterpenoid
dc.type article
dc.type.genre article
dspace.entity.type Publication
relation.isAuthorOfPublication 498a24ec-81d7-4bee-b145-323d38e7a392
relation.isOrgUnitOfPublication c70f85ae-e0cd-4dce-96b5-4388aac08b3f
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