N-Inversion-Rotation versus Rotation-N-Inversion Paths in the Fasicularin Models

Papiya Majumdar, Sanjay Dutta, Rainer Glaser,* and Kent Gates*

Department of Chemistry, University of Missouri-Columbia, Columbia, Missouri, 65211 (USA)


The free CHIME plugin is required for the display of the pdb files of the following structures.


Matrix 1. Substates, Reaction Transition State, and Products
Molecule Gas-Phase, R = Me Solution, R = Me Gas-Phase, R = H Solution, R = H
Chair
pre-inversion
Boat
pre-inversion
Boat
post-inversion
Reaction
Transition
State
Ion Pair
Adduct
Aziridinium
Ion
SCN-
Anion


Matrix 2. Inversion Transition States
Conformation Gas-Phase, R = Me Solution, R = Me Gas-Phase, R = H Solution, R = H
R-SCN
Conformer 1
R-SCN
Conformer 2
R-SCN
Conformer 3


Matrix 3. Inversion 2 Transition States
Conformation Gas-Phase, R = Me Solution, R = Me Gas-Phase, R = H Solution, R = H
R-SCN
Conformer 1
R-SCN
Conformer 2
R-SCN
Conformer 3


Matrix 4. Rotation Transition States
Conformation Gas-Phase, R = Me Solution, R = Me Gas-Phase, R = H Solution, R = H
R-SCN
Conformer 1
R-SCN
Conformer 2
R-SCN
Conformer 3


Matrix 5. NIR Transition State Vectors Computed for the Gas-Phase --- PARENT
N-Inversion in B-Chair
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3
B-Chair to B-Boat
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3
N-Inversion in B-Boat
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3


Matrix 6. NIR Transition State Vectors Computed for the Gas-Phase --- METHYL
N-Inversion in B-Chair
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3
B-Chair to B-Boat
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3
N-Inversion in B-Boat
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3


Matrix 7. NIR Transition State Vectors Computed for the Solution-Phase --- PARENT
N-Inversion in B-Chair
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3
B-Chair to B-Boat
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3
N-Inversion in B-Boat
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3


Matrix 8. NIR Transition State Vectors Computed for the Solution-Phase --- METHYL
N-Inversion in B-Chair
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3
B-Chair to B-Boat
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3
N-Inversion in B-Boat
NCS-C Conformer #1 NCS-C Conformer #2 NCS-C Conformer #3