期刊
CHEMICAL SCIENCE
卷 8, 期 2, 页码 1442-1449出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6sc03745c
关键词
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资金
- National Science Foundation [CHE-1565933, CHE-030089]
- Department of Education's Graduate Assistance in Areas of National Need (GAANN) fellowship
Byproducts of chemical reactions are generally thought to result from the competition between two reaction pathways, each with its own rate-determining transition state structure. We show here, however, that pathways with a single transition state structure followed by a post-transition state bifurcation may also be a source of undesired products, especially those whose appearance is unexpected. The viability of this scenario for intramolecular C-H insertion reactions affording b-lactones via Rh-carbenoid intermediates is assessed through quantum chemical calculations on potential energy surfaces and quasi-classical molecular dynamics simulations. It appears that, in these cases, the rhodium catalyst is to blame for the accessibility of a second, unintended, pathway following the transition state structure for b-lactone formation that leads to fragmentation to a ketene and carbonyl compound. If an unexpected product is formed via a post-transition state bifurcation, conventional strategies for suppressing its formation are unlikely to succeed. Guidelines for recognizing the presence of a posttransition state bifurcation are described here, along with hints at means for controlling product distributions.
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