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Title: Rotation‐Inversion Isomerization of Tertiary Carbamates: Potential Energy Surface Analysis of Multi‐Paths Isomerization Using Boltzmann Statistics
Abstract

Potential energy surface (PES) analyses at the SMD[MP2/6–311++G(d,p)] level and higher‐level energies up to MP4(fc,SDTQ) are reported for the fluorinated tertiary carbamateN‐ethyl‐N‐(2,2,2‐trifluoroethyl) methyl carbamate (VII) and its parent systemN,N‐dimethyl methyl carbamate (VI). Emphasis is placed on the analysis of the rotational barrier about the CN carbamate bond and its interplay with the hybridization of theN‐lone pair (NLP). All rotational transition state (TS) structures were found by computation of 1D relaxed rotational profiles but only 2D PES scans revealed the rotation‐inversion paths in a compelling fashion. We found four unique chiral minima ofVII, one pair each ofE‐andZ‐rotamers, and we determined theeightunique rotational TS structures associated with every possibleE/Z‐isomerization path. It is a significant finding that all TS structures featureN‐pyramidalization whereas the minima essentially contain sp2‐hybridized nitrogen. We will show that the TS stabilities are affected by the synergetic interplay between NLP/CO2repulsion minimization, NLP→σ*(CO) negative hyperconjugation, and two modes of intramolecular through‐space electrostatic stabilization. We demonstrate how Boltzmann statistics must be applied to determine the predicted experimental rotational barrier based on the energetics of all eight rotamerization pathways. The computed barrier forVIIis in complete agreement with the experimentally measured barrier of the very similar fluorinated carbamateN‐Boc‐N‐(2,2,2‐trifluoroethyl)‐4‐aminobutan‐1‐olII. NMR properties ofVIIwere calculated with a variety of density functional/basis set combinations and Boltzmann averaging over theE‐andZ‐rotamers at our best theoretical level results in good agreement with experimental chemical shifts δ(13C) andJ(13C,19F) coupling constants ofII(within 6 %).

 
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NSF-PAR ID:
10389348
Author(s) / Creator(s):
 ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
ChemPhysChem
Volume:
24
Issue:
1
ISSN:
1439-4235
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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