Open AccessThe Influence of Substitution on Thiol-Induced Oxanorbornadiene Fragmentation
Author(s) -
Lucrezia De Pascalis,
Mei-Kwan Yau,
Dennis Svatunek,
Zhuoting Tan,
Srinivas Tekkam,
K. N. Houk,
M. G. Finn
Publication year - 2021
Publication title -
organic letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.94
H-Index - 239
eISSN - 1523-7060
pISSN - 1523-7052
DOI - 10.1021/acs.orglett.1c01164
Subject(s) - chemistry , fragmentation (computing) , furan , electrophile , thiol , stereochemistry , density functional theory , computational chemistry , organic chemistry , catalysis , operating system , computer science
Oxanorbornadienes (ONDs) undergo facile Michael addition with thiols and then fragment by a retro-Diels-Alder (rDA) reaction, a unique two-step sequence among electrophilic cleavable linkages. The rDA reaction rate was explored as a function of the furan structure, with substituents at the 2- and 5-positions found to be the most influential and the fragmentation rate to be inversely correlated with electron-withdrawing ability. Density functional theory calculations provided an excellent correlation with the experimentally measured OND rDA rates.