Biosynthesis of lycosantalonol, a cis-prenyl derived diterpenoid

Biblio

Publication Type:

Journal Article

Source:

J Am Chem Soc, Volume 136, Number 49, p.16951-3 (2014)

ISBN:

0002-7863

Accession Number:

25406026

Abstract:

Terpenoid natural products are generally derived from isoprenyl diphosphate precursors with trans double-bond configuration, and no diterpenoid derived from the cisoid precursor (Z,Z,Z)-nerylneryl diphosphate (1) 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 1, in a pathway featuring a number of interesting transformations. Compound 1 is first cyclized to a tricyclene core ring structure analogous to that found in alpha-santalene, with the resulting diterpene termed here lycosantalene (2). 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 2 is then further transformed to an alpha-hydroxy ketone moiety via an epoxide intermediate (3). Oxygen labeling studies indicate 3 undergoes oxidative conversion to lycosantalonol (4). Thus, in addition to elucidating the cisoid origins of 4, this work has further provided mechanistic insight into the interesting transformations required for its production.

Notes:

1520-5126<br/>Zi, Jiachen<br/>Matsuba, Yuki<br/>Hong, Young J<br/>Jackson, Alana J<br/>Tantillo, Dean J<br/>Pichersky, Eran<br/>Peters, Reuben J<br/>GM076324/GM/NIGMS NIH HHS/United States<br/>Journal Article<br/>Research Support, N.I.H., Extramural<br/>Research Support, U.S. Gov't, Non-P.H.S.<br/>United States<br/>J Am Chem Soc. 2014 Dec 10;136(49):16951-3. doi: 10.1021/ja508477e. Epub 2014 Nov 21.