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A Metathesis Route to (+)‐Orientalol F, a Guaiane Sesquiterpene from Alisma Orientalis
Author(s) -
Zahel Martin,
Wang Yuzhou,
Jäger Anne,
Metz Peter
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201601197
Subject(s) - chemistry , wittig reaction , regioselectivity , allylic rearrangement , epoxide , aldehyde , ring closing metathesis , epimer , metathesis , ylide , claisen rearrangement , ketone , stereochemistry , intramolecular force , organic chemistry , catalysis , polymer , polymerization
The synthesis of (+)‐orientalol F ( 1 ) started with aldehyde 6 , which is available from ( R )‐limonene in two steps. Wittig reaction of 6 with unsaturated ylide 7 to give a tetraene, and subsequent ring‐closing metathesis yielded hydroazulene 4 , selective epoxidation of which gave epoxy ester 3 . After generation of the requisite isopropyl unit and regioselective reductive epoxide opening, the derived dienol 2 was used for the installation of the oxygen bridge through intramolecular oxymercuration followed by oxidative demercuration. The resulting allylic alcohol epimers 15 and 16 were readily converted into the target natural product 1 by oxidation/reduction sequences.