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Type II Intramolecular [5+2] Cycloaddition: Facile Synthesis of Highly Functionalized Bridged Ring Systems
Author(s) -
Mei Guangjian,
Liu Xin,
Qiao Chuang,
Chen Wei,
Li Chuangchuang
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201410806
Subject(s) - cycloaddition , bicyclic molecule , intramolecular force , dodecane , undecane , ring (chemistry) , decane , chemistry , selectivity , substrate (aquarium) , combinatorial chemistry , stereochemistry , organic chemistry , catalysis , oceanography , geology
A type II intramolecular oxidopyrylium‐mediated [5+2] cycloaddition reaction allows the efficient and diastereoselective formation of various highly functionalized and synthetically challenging bridged seven‐membered ring systems (such as bicyclo[4.4.1]undecane, bicyclo[4.3.1]decane, bicyclo[5.4.1]dodecane, and bicyclo[6.4.1]]tridecane). This simple, thermal, direct transformation has a broad substrate scope and is high yielding, with high functional‐group tolerance and unique endo selectivity. The highly strained tricyclic cores of ingenol mebutate (picato) and cyclocitrinol are synthesized efficiently and diastereoselectively using this methodology.