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Two‐Step Synthesis of Heptacyclo[6.6.0.0 2,6 .0 3,13 .0 4,11 .0 5,9 .0 10,14 ] tetradecane from Norbornadiene: Mechanism of the Cage Assembly and Post‐synthetic Functionalization
Author(s) -
Zieliński Adam,
Marset Xavier,
Golz Christopher,
Wolf Lawrence M.,
Alcarazo Manuel
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202010766
Subject(s) - chemistry , dimer , stereochemistry , crystallography , organic chemistry
A selective and scalable two‐step approach to the dimerization of norbornadiene (NBD) into its thermodynamically most stable dimer, heptacyclo[6.6.0.0 2,6 .0 3,13 .0 4,11 .0 5,9 .0 10,14 ] tetradecane, (HCTD) is reported. Calculations indicate that the reaction starts with the Rh‐catalyzed stepwise homo Diels–Alder cyclisation of NBD into its exo‐cis‐endo dimer. Treatment of this compound with acid promotes its evolution to HCTD via a [1,2]‐sigmatropic rearrangement. The assemblies of 7,12‐disubstituted cages from 7‐(alkyl/aryl) NBDs, as well as the selective post‐synthetic C−H functionalization of the core HCTD scaffold at position C1, or positions C1 and C4 are described.