10.1002/anie.201711277
Angewandte Chemie International Edition
COMMUNICATION
1.25
1.00
0.75
Δ
0.50
0.25
0.00
0.00 0.25 0.50 0.75 1.00 1.25
Measured ΔΔG‡ (kcal/mol)
2.0
1.5
1.0
0.5
0.0
0.0
0.5
1.0
1.5
2.0
Measured ΔΔG‡ (kcal/mol)
Figure 1. [a] Multidimensional correlation analysis for the set of catalysts 1a-1h and [b] for the set of substrates 4a-4h. [c] TS-R and TS-S
computed at the wB97XD/6-31G(d) level of theory. wB97XD/6-311+G(2d,p)[PCM=Tol] energies are reported. The substrate is highlighted
in green and interatomic distances are shown as dashed lines. [d] electron density map of the uncatalyzed TS of 6d.
organocatalytic C-S bond formations, see: (d) P. Chauhan, S. Mahajan,
multidimensional correlation techniques, which revealed that a
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set of subtle yet important NCIs are responsible for the observed
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We gratefully acknowledge NIGMS (R35 GM118190 to F. D. T. and
R01 GM121383 to M. S. S.) for financial support of this work. K.K. is
grateful to the JSPS for their scholarship support. Computations
were performed at the Center for High Performance Computing
(CHPC) of the University of Utah.
Keywords: phase-transfer catalysis • chiral anions • Pummerer
reaction • N,S-acetal • synthetic method • theoretical study
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