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Enantioselective 1,3‐Dipolar [6+4] Cycloaddition of Pyrylium Ions and Fulvenes towards Cyclooctanoids
Author(s) -
McLeod David,
CherubiniCelli Alessio,
Sivasothirajah Nisanhi,
McCulley Christina H.,
Christensen Mette Louise,
Jørgensen Karl Anker
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001369
Subject(s) - enantioselective synthesis , chemistry , cycloaddition , stereoselectivity , catalysis , organocatalysis , amine gas treating , fulvenes , combinatorial chemistry , computational chemistry , organic chemistry
Organocatalytic enantioselective 1,3‐dipolar [6+4] cycloadditions of pyrylium ion intermediates with fulvenes promoted by a chiral primary amine catalyst have been developed to proceed in moderate to good yields and high enantioselectivities. The resultant chiral bicyclo[6.3.0]undecane scaffold containing a transannular bridging ether is densely functionalised providing a rigid scaffold for further manipulations. Computational studies give important insights into the role of the primary amine catalyst. Analysis of the reaction shows that the catalytic reaction proceeds in a step‐wise manner and rationalises the stereochemical outcome of the reaction. Several stereoselective complexity‐generating transformations, facilitated by the diverse functional groups and transannular bridge, are presented, highlighting the versatility of the core towards a number of the cyclooctanoid natural products.