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Towards an Effective Synthesis of Difunctionalized Heptacyclo [6.6.0.0 2,6 .0 3,13 .0 4,11 .0 5,9 .0 10,14 ]tetradecane: Ligand Effects on the Cage Assembly and Selective C−H Arylation Reactions
Author(s) -
Marset Xavier,
RecortFornals Martí,
Kpante Malkaye,
Zieliński Adam,
Golz Christopher,
Wolf Lawrence M.,
Alcarazo Manuel
Publication year - 2021
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202100481
Subject(s) - chemistry , dimer , regioselectivity , tetradecane , chelation , stereochemistry , medicinal chemistry , crystallography , catalysis , organic chemistry
A series of strong π‐acceptor polyfluorinated and dicationic chelating phosphines have been synthesized and evaluated in the Rh‐catalysed dimerization of norbornadiene (NBD) into its thermodynamically more stable dimer, heptacyclo[6.6.0.0 2,6 .0 3,13 .0 4,11 .0 5,9 .0 10,14 ] tetradecane (HCTD). While dicationic ligands direct the dimerization towards HCTD, by the use of neutral polyfluorinated ancillary ligands endo‐endo ‐heptacyclo [8.4.0.0 2,12 .0 3,8 .0 4,6 .0 5,9 .0 11,13 ]tetradecane (BINOR−S) is selectively obtained. In addition, a selective Pd‐catalysed arylation at position C8 of the HCTD framework is achieved by the use of a picolylamide directing group previously attached at C1. Theoretical calculations have been performed to understand the origin of that regioselectivity.