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Highly Diastereoselective, Biogenetically Patterned Synthesis of (+)‐(1 S ,6 R )‐Volvatellin (=(+)‐(4 R ,5 S )‐5‐Hydroxy‐4‐(5‐methyl‐1‐methylenehex‐4‐en‐2‐ynyl)cyclohex‐1‐ene‐1‐carbaldehyde)
Author(s) -
Mancini Ines,
Guella Graziano,
Pietra Francesco
Publication year - 2000
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/(sici)1522-2675(20000412)83:4<694::aid-hlca694>3.0.co;2-3
Subject(s) - chemistry , ene reaction , stereochemistry , absolute configuration , enzyme , organic chemistry
The synthesis of volvatellin ( 4a ), previously isolated from a herbivorous marine mollusk, was achieved with high diastereoselectivity from putative dietary oxytoxin‐1 ( 2 ). A biogenetically patterned carbonyl‐ene route was chosen, proceeding from 2 predominantly via the trans cyclization product 3 without the use of enzymes. This challenges the involvement of enzymes in the formation of 4a in nature. The optical purity and absolute configuration (1 S ,4 S ,6 R ), assigned to 3 from high‐field 1 H‐NMR examination of its Mosher (MTPA) esters 6 , was retained on its chemical conversion to (+)‐(1 S ,6 R )‐configured 4a and is consistent with the (4 S ) configuration previously established for caulerpenyne ( 1 ).