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Exploiting Non‐Covalent Interactions in Synthesis: Macrocyclization Employing Amide‐Based Auxiliaries
Author(s) -
ElAzizi Yassir,
Zakarian Joseph E.,
Bouillerand Lisa,
Schmitzer Andreea R.,
Collins Shawn K.
Publication year - 2008
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.200800365
Subject(s) - chemistry , amide , olefin metathesis , stereochemistry , linkage (software) , covalent bond , metathesis , olefin fiber , conformational isomerism , combinatorial chemistry , organic chemistry , molecule , polymerization , catalysis , polymer , biochemistry , gene
Efficient macrocyclic olefin and en‐yne metathesis can be conducted employing benzyl ester auxiliaries that engage in quadrupolar interactions. The use of amide linkers in place of esters results in higher overall yields. Computational studies suggest that amide auxiliaries stabilize conformers conducive to macrocyclization over 22 times more efficiently than an ester linkage. Molecular modelling studies also suggest a preference for engaging in quadrupolar interaction for the amide auxiliaries, in contrast to the lone‐pair (lp):π interactions predicted for ester‐based auxiliaries.