PT  - JOURNAL ARTICLE
AU  - Jianyu Zhang
AU  - Judith P. Klinman
TI  - CH···O Interactions Are Not the Cause of Trends in Reactivity and Secondary Kinetic Isotope Effects for Enzymatic S<sub>N</sub>2 Methyl Transfer Reactions
AID  - 10.1101/071043
DP  - 2016 Jan 01
TA  - bioRxiv
PG  - 071043
4099  - http://biorxiv.org/content/early/2016/09/01/071043.short
4100  - http://biorxiv.org/content/early/2016/09/01/071043.full
AB  - Compaction matters SN2 substitution represents an important class of reaction for both chemical and biological systems. The ability to assess enzymatic transition state structure within this class of reaction remains a major experimental challenge. Here, we comment on and compare the relative impact of compaction along the axis of reaction to the impact of an orthogonal CH···O hydrogen bonding interaction. The latter is concluded to play a limited role in determining relative reaction rates and secondary KIEs derived from experimental structure-activity correlations.