Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
This journal is © The Royal Society of Chemistry 2016
Electronic Supporting Information
Cross-Benzoin and Stetter-Type Reactions Mediated by KOtBu-DMF
via Electron-Transfer process
Daniele Ragno,a Anna Zaghi,a Graziano Di Carmine,a Pier Paolo Giovannini,a Olga Bortolini,a
Marco Fogagnolo,a Alessandra Molinari,a Alessandro Venturini,*b and Alessandro Massi*a
a
Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Ferrara, Via Fossato di
Mortara 17, I-44121 Ferrara (Italy)
b
ISOF-CNR, Area della Ricerca di Bologna, Via P. Gobetti 101, I-40129 Bologna (Italy)
alessandro.massi@unife.it; alessandro.venturini@isof.cnr.it
Table of Contents
MS experiments (Figures S1-S2)
S2
EPR experiments (Figures S3-S5)
S3
Computational methods, Cartesian coordinates and energies in Hartree for species calculated
S5
NMR spectra of new compounds
S16
References
S22
S1
Mass spectrometric experiments
The mass spectrometric investigations were carried out on a LCQ Duo (ThermoQuest, San Jose,
CA, USA), equipped with an electrospray ionization source operating in negative-ion mode.
Instrumental parameters: capillary voltage -10 V, spray voltage 4.50 kV, capillary temperature of
150 °C, mass scan range from m/z 50 to 1200; N2 was used as sheath gas. The samples were
injected into the spectrometer by a syringe pump at a constant flow rate of 8 µL/min using the
appropriate eluting solvent.
Figure S1. Full scan spectrum of the benzoin-like reaction of 1a (0.5 M), 2a (0.5 M) in DMF with
KOtBu (0.125 M) showing the presence of anion E (m/z 90) and isobaric species I-III(E) (m/z 300).
Figure S2. MS/MS mass spectrum of the deuterated adduct III(E)-d obtained from DMF-d7
solutions of 1a (0.5 M), 2a (0.5 M) and KOtBu (0.125 M).
S2
EPR experiments
EPR investigation was carried out with a Bruker ER200 MRD spectrometer calibrated with α,α’diphenylpicrylhydrazyl (dpph, resonance at 3457.41 G, g = 2.0023) and equipped with a TE201
resonator (microwave frequency of 9.4 GHz). A flat quartz cell was used for all the experiments.
Samples were DMF solutions containing KOtBu (0.125 M) to which benzyl 1a (0.5 M) and
aldehyde 2a (0.5 M) were added stepwise and when necessary. In the case of EPR spin trapping
experiments, DMF solutions contain from the beginning a-phenyl-N-tert-butyl nitrone (PBN, 0.5
M) as radical trap. When requested benzyl 1a (0.5 M) and aldehyde 2a (0.5 M) were progressively
added.
Figure S3. Fixed-field EPR signal intensity of a radical species (g= 2.0017) in time obtained by the
addition of aldehyde 2a (0.5 M) to a DMF solution of KOtBu (0.125 M) and of benzil 1a (0.5 M).
Figure S4. Fixed-field EPR signal intensity of the paramagnetic adduct [PBN-benzyl anion radical
V]• in time. (●) DMF solution containing KOtBu (0.125 M), benzil 1a (0.5 M) and PBN (0.5 M).
(▲) the same as before with the addition of aldehyde 2a (0.5 M).
S3
Figure S5. Anaerobic EPR spectrum of a DMF solution containing KOtBu (0.125 M) and PBN (0.5
M).
S4
Computational methods, Cartesian coordinates and energies in Hartree for species calculated
DFT calculations were carried out with the Truhlar M06 hybrid functional,1 together with the 6-31+
G(d,p) basis set within the framework of the Gaussian 09 suite of programs.2 All the molecular
structures were fully optimized by using the PCM continuum model (N,N-dimethylformamide and
dimethylsulfoxide)3 and the Berny analytical gradient optimization method, whereby the stationary
points were characterized by frequency calculation. Thermochemical analysis (free energies DDG)
was performed at 298.15 K, starting from the frequency calculations.
Electronic energies (E, u.a.), Gibbs free energies (DG, u.a.), and fully optimized structures [M06//631+G(d,p) level using PCM continuum model (N,N-dimethylformamide and dimethylsulfoxide)]
are reported in the next pages (pp. S5-S14).
S5
Structures of Figure 3
TS reactants- I(E)
1a
E = -1013.80292
DG = -1013.53566
E = -689.51998
DG = -689.36149
C
O
C
C
C
C
C
C
H
H
H
H
H
C
O
C
C
C
C
C
C
H
H
H
H
H
-0.868844
-0.179584
-1.618674
-1.501990
-2.225261
-3.074060
-3.199710
-2.471765
-0.839556
-2.133648
-3.641473
-3.862277
-2.570196
-0.862894
-0.162156
-1.616089
-1.489398
-2.215464
-3.077001
-3.212607
-2.481938
-0.817082
-2.116133
-3.646586
-3.885062
-2.588200
-0.494326
-1.497915
-0.140331
-0.953407
-0.652366
0.456605
1.265450
0.970338
-1.814750
-1.278930
0.690780
2.126359
1.607084
0.480119
1.475682
0.134804
0.946476
0.653801
-0.445295
-1.252632
-0.965940
1.800112
1.279264
-0.672904
-2.105831
-1.601503
C
C
C
C
C
C
C
O
C
O
C
C
C
C
C
C
O
C
N
C
O
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
0.135532
0.254542
-1.078274
-2.213509
-3.357817
-3.372863
-2.245241
-1.098263
-2.178466
-4.240897
-4.270210
-2.260793
-0.221126
1.314478
1.195081
2.528701
3.663867
4.808577
4.824097
3.696547
2.549165
3.628456
5.691604
5.721758
3.712468
1.672084
E
E = -324.27277
DG = -324.18874
C -1.605229 -0.848889 -0.290468
N -0.643114 0.221028 -0.429466
C -0.909573 1.279770 0.519908
C 0.764065 -0.252725 -0.407283
O 1.656935 0.680661 -0.576519
H 0.766997 -1.090730 -1.154536
H -2.611920 -0.490390 -0.545750
H -1.354575 -1.670419 -0.974704
H -1.643083 -1.263229 0.736222
H -1.885681 1.736745 0.308411
H -0.930214 0.920469 1.568603
H -0.136215 2.049365 0.433906
O 0.993418 -0.983299 0.872501
H 1.598088 -0.386835 1.333316
1.821514
1.327215
2.170695
3.483801
3.968057
3.132054
-0.051995
-0.358819
-1.182273
-1.020620
-2.515299
-2.710691
-3.992303
-5.090196
-4.904355
-3.623789
0.151896
1.058643
1.444336
2.457524
0.604906
1.954380
2.015011
2.753542
2.071395
3.369520
2.212785
2.869659
1.200565
0.253711
1.784063
4.127214
4.993751
3.508801
1.187340
-3.465813
-5.757355
-6.090269
-4.135237
-1.845847
-1.520647
-1.407429
-1.714647
-2.125374
-2.230668
-1.926074
-0.927358
-0.642629
-1.244954
-2.119887
-0.605025
0.629231
1.157895
0.460918
-0.768748
-1.293616
0.928596
1.652757
2.874280
3.626272
2.110695
2.516949
1.078929
4.500779
3.971580
3.020593
3.426215
1.889024
1.959773
1.309557
-1.619122
-2.359783
-2.545934
-1.999018
-1.255149
-2.252011
-1.316924
0.877613
2.123134
1.179695
-0.987837
0.317222
1.387362
1.167460
-0.133088
-1.209051
0.641901
1.808998
-0.340956
-1.181821
-0.162852
0.469286
0.583810
0.081272
-0.548783
-0.673561
-0.468122
0.168104
-0.561333
0.159978
1.467798
-1.873276
0.368821
-0.431442
1.121878
0.349471
-2.428601
-1.807800
-2.434533
1.886904
2.399392
2.012477
-0.311507
-2.226956
-1.827329
-1.162654
-0.941571
0.178585
1.064181
0.823241
IE
E = -1013.81590
DG = -1013.54477
C
N
C
S6
1.521792
0.861926
1.557555
4.081183 -0.044428
2.911482 -0.607532
2.490697 -1.815103
C
O
O
H
H
H
H
H
H
H
H
C
C
O
C
C
C
C
C
C
H
H
H
H
H
O
C
C
C
C
C
C
H
H
H
H
H
0.813878
0.198357
0.105153
1.853188
1.545783
0.979831
2.566770
1.563228
2.610490
1.052532
0.034323
0.223777
-0.930071
0.020773
1.581844
2.472381
3.718583
4.080389
3.188063
1.950021
2.173738
4.407613
5.050739
3.461530
1.257402
-0.731465
-2.324669
-3.283400
-4.601703
-4.985720
-4.042862
-2.720524
-2.974857
-5.329757
-6.016537
-4.338419
-1.989629
1.836714
2.298183
0.774397
1.497104
4.874593
4.446128
3.862886
3.318670
2.208380
1.636103
1.448370
-0.471875
-1.379529
-0.295191
-1.078932
-1.474566
-2.009844
-2.161214
-1.775164
-1.239467
-1.348597
-2.308844
-2.577546
-1.892060
-0.932081
-2.583749
-0.847860
-1.715683
-1.309586
-0.024070
0.846865
0.444272
-2.717913
-1.995612
0.298381
1.850058
1.130846
C
C
C
C
O
C
O
N
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
0.356630
1.525667
-0.198065
0.603253
-0.798609
0.830035
0.256011
-2.531682
-1.610492
-2.271166
2.006319
0.599629
0.118707
1.900553
0.225808
1.219015
0.886941
-0.448802
-1.451677
-1.113059
2.257634
1.674651
-0.711069
-2.498561
-1.896349
-0.011788
-0.020478
-0.560633
-0.731525
-0.353633
0.189422
0.351211
-0.847709
-1.158355
-0.482576
0.488210
0.764077
2.784107
3.760914
3.524260
2.311012
0.190718
-0.735624
-1.796247
-0.016046
-0.914965
1.054338
-0.035339
-0.138797
-1.478425
-2.736694
-2.647327
2.107181
4.284581
4.704671
2.964053
0.803370
-1.099946
-2.210259
-1.409988
-1.687546
-0.338929
1.756291
0.663935
1.594855
1.603252
0.608924
-0.622236
-0.859621
0.435418
0.119080
1.004547
0.203330
-0.011938
-0.784573
-1.943897
-1.941584
-0.218860
1.480741
1.443670
-1.824483
-1.399728
0.792599
2.564669
2.134360
-0.915440
0.829044
-1.003033
0.758561
0.032794
-0.617122
-1.819522
-0.699821
II(E)
E = -1013.79632
DG = -1013.52900
C
C
C
C
C
C
C
O
C
O
C
C
C
C
C
C
O
C
O
N
C
TS1(E)
E = -1013.79682
DG = -1013.52580
C
C
C
C
C
C
C
O
C
O
C
C
-1.554311
-1.595546
-0.984726
-0.342658
1.696794
2.716179
2.721171
3.967036
5.092633
3.999773
-1.991884
-4.469472
-5.661382
-4.350190
-1.866785
0.120233
-1.014972
-2.104190
-2.030431
-0.875252
2.538372
1.825228
5.043639
5.121807
6.022847
3.178718
3.918362
4.948173
-2.512833 -0.622258 -1.191652
-1.766997 -1.323425 -0.239840
-2.447412 -2.088893 0.712734
-3.838978 -2.141330 0.726978
-4.574484 -1.436783 -0.224300
-3.904901 -0.682770 -1.186912
-0.263445 -1.291252 -0.157727
0.326551 -2.385228 0.188497
0.408142 0.035589 -0.125963
0.323981 -0.486361 -1.408817
-0.303509 1.331171 0.130197
-0.905270 1.574837 1.364692
S7
-2.493403
-1.691433
-2.304633
-3.689664
-4.484325
-3.880583
-0.186921
0.437376
0.431595
0.301581
-0.362665
-0.562604
-1.311599
-1.861896
-1.661346
-0.918397
1.731634
2.753974
2.705468
4.006614
5.131728
-1.064633
-1.348821
-1.753215
-1.856899
-1.575847
-1.185298
-1.273851
-2.356857
0.086699
-0.517722
1.336062
1.800423
2.950341
3.652665
3.194977
2.037731
0.343102
-0.621760
-1.596854
0.094124
-0.828938
-1.273116
-0.167604
1.023032
1.112073
0.000313
-1.192722
-0.191336
0.161233
-0.198520
-1.449794
0.034099
1.336891
1.567512
0.494721
-0.805691
-1.033523
0.274553
0.095805
1.068138
0.179110
0.115612
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
4.116249
-1.680571
-4.150746
-5.566756
-4.491932
-2.022597
-0.774782
-2.090565
-2.448546
-1.468480
-0.132407
1.839647
2.619592
5.138050
5.105043
6.063937
5.073744
3.310548
4.077585
1.072443
-1.986911
-2.162030
-1.661436
-0.967666
-0.742364
1.658309
3.736816
4.550840
3.300141
1.247743
-2.066299
-1.073927
-1.413087
-1.527043
-0.256508
1.596172
1.806896
0.595656
H
H
H
H
H
H
H
H
H
H
-0.894321
1.884453
2.049272
0.065046
-2.066290
-2.199047
-2.043253
-1.645886
0.674074
2.585555
2.171341
0.850333
-0.911737
-0.826946
0.953879
0.164336
-0.806125
-0.830505
-1.894657
0.812847
1.166258
2.348696
3.126304
2.772728
1.598992
0.405454
-0.953527
-1.763618
-2.070137
0.579215
1.324124
0.769626
-0.609836
-1.086417
-0.198538
1.174525
1.654490
2.366850
-2.961752
-3.776634
-3.744327
-1.305774
-2.158955
-0.575878
1.872424
2.723214
2.651797
4.026052
3.386060
-2.292553
-1.825965
0.661425
-0.263345
0.639910
1.335871
-1.354626
0.242869
-1.091618
1.989493
E = -1013.76818
DG = -1013.50027
C
O
C
C
C
C
C
C
H
H
H
H
H
O
C
O
C
C
C
C
C
C
H
H
H
H
H
C
N
H
O
C
C
H
H
H
H
H
H
H
E = -1013.76244
DG = -1013.49344
2.494728
1.552964
1.834329
2.951036
3.854044
3.606542
0.352035
0.399008
1.202527
0.523816
-0.232054
-1.358340
-2.441624
-2.625320
-3.723334
-4.644154
-4.471098
-3.386207
-1.487703
1.528283
0.373971
2.546896
-1.900890
-3.860854
-5.497197
-5.187470
-3.250514
1.154024
3.126235
4.726910
1.287659
-0.094521
-1.228508
-4.548073
-3.112910
-4.203954
-4.537581
-4.290837
-3.153213
-1.231980
III(E)
TS2(E)
C
C
C
C
C
C
C
O
C
O
O
C
C
C
C
C
C
C
O
N
C
C
H
H
H
H
H
H
H
H
4.299385
2.324371
2.140252
2.886169
3.410172
2.181183
0.685192
-0.064246
-0.396950
0.187743
-1.247983
-0.240580
0.496338
0.217332
-0.789641
-1.510948
-0.062635
-0.397867
0.425341
1.633960
1.261618
1.107188
0.253507
0.088573
-0.618843
-1.175647
-1.005058
-0.280178
1.724268
-0.277393
-0.629912
0.400162
0.502669
-0.737391
-1.734709
-1.432276
-0.131138
1.289188
0.807081
-1.001071
S8
-1.649869
-1.622223
-2.916362
-2.995764
-4.207610
-5.349904
-5.278578
-4.069499
-2.111712
-4.261500
-6.295078
-6.167398
-4.000994
-0.577393
0.737372
1.382020
1.462018
0.841575
1.577406
2.960990
3.596617
2.876837
-0.234229
1.055991
3.529428
4.677587
3.396882
1.784296
2.823177
2.180162
0.685175
3.470815
2.423799
4.370587
3.775878
2.820675
3.320584
1.753065
1.917273
-0.014915
0.768152
1.773224
0.187135
-1.118425
-1.620029
-0.820838
0.479086
0.977803
-1.750345
-2.638510
-1.212387
1.105032
1.988505
0.086634
0.351785
-0.895626
1.400793
2.442205
3.500364
3.578877
2.548960
1.490602
2.420339
4.277791
4.410243
2.572954
0.703547
-1.495049
-2.435653
-0.720452
-2.137737
-2.904318
-3.543463
-3.470823
-2.051155
-3.559104
-4.088145
-4.254480
-3.163855
-1.473385
-0.746817
-1.440990
-0.221758
0.274829
0.737293
0.715945
0.217675
-0.254268
0.279411
1.113964
1.084604
0.197779
-0.648949
-0.360978
-0.946632
-1.042165
-0.289111
0.450873
0.973538
0.805396
0.099212
-0.430032
0.605626
1.531822
1.215835
-0.036788
-0.974946
0.166883
-0.099932
0.845484
0.795617
1.112333
-0.955338
0.846041
1.729210
1.720040
-1.271952
-0.442489
-1.846417
0.879251
Structures of Figure 6
H
IX
TS IX-2g
E = -689.720593
DG = -689.56415
E = -1035.07880
DG = -1034.81931
C
O
C
C
C
C
C
C
H
H
H
H
H
C
O
C
C
C
C
C
C
H
H
H
H
H
-0.868841
-0.179583
-1.618643
-1.501947
-2.225244
-3.074088
-3.199733
-2.471737
-0.839493
-2.133620
-3.641544
-3.862281
-2.570125
-0.862945
-0.162210
-1.616113
-1.489387
-2.215432
-3.076995
-3.212637
-2.481980
-0.817034
-2.116058
-3.646588
-3.885111
-2.588277
-0.494330
-1.497910
-0.140329
-0.953410
-0.652381
0.456562
1.265415
0.970330
-1.814736
-1.278935
0.690707
2.126336
1.607110
0.480164
1.475727
0.134843
0.946471
0.653764
-0.445312
-1.252605
-0.965885
1.800079
1.279176
-0.672923
-2.105789
-1.601397
0.135534
0.254564
-1.078296
-2.213531
-3.357827
-3.372850
-2.245239
-1.098275
-2.178485
-4.240912
-4.270178
-2.260787
-0.221157
1.314466
1.195047
2.528703
3.663900
4.808613
4.824109
3.696535
2.549149
3.628517
5.691670
5.721765
3.712428
1.672031
C 0.268305 2.014169
O 1.378007 2.519124
H -0.641292 2.654029
C 0.000000 0.571178
C -1.326963 0.130471
C -1.608624 -1.231679
C -0.561444 -2.151406
C 0.766275 -1.715410
C 1.048926 -0.357074
H -2.133888 0.862274
H -2.639057 -1.576747
H -0.779298 -3.216686
H 1.575657 -2.440839
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
0.000000
C
C
C
C
C
C
C
O
C
C
C
C
C
C
C
O
H
H
H
H
H
H
H
H
H
H
C
O
H
C
C
C
C
C
C
H
H
H
H
H
2g
E = -345.35472
DG = -345.27556
2.074963
-1.373562
-1.014153
-1.943186
-3.165804
-3.501224
-2.593667
0.245319
0.379115
1.481740
2.807352
3.813425
5.066002
5.347227
4.360607
3.099384
1.484507
3.587308
5.825139
6.329035
4.572608
2.305944
-1.673244
-3.860936
-4.451869
-2.842773
-0.694223
0.109835
0.295814
0.918227
-1.212235
-1.373634
-2.618587
-3.733883
-3.582498
-2.337033
-0.503204
-2.718885
-4.705656
-4.442549
-2.208961
0.003485
2.016923
1.217668
1.118646
1.787335
2.583029
2.687096
0.390473
-0.315110
1.090511
0.371231
0.837095
0.235878
-0.845460
-1.318985
-0.723309
2.224217
1.682046
0.608909
-1.314464
-2.161861
-1.070532
0.482385
1.687498
3.112903
3.295834
2.080175
-0.774120
-0.244398
-1.438780
-1.439388
-2.402177
-2.972278
-2.605286
-1.667721
-1.099643
-2.688597
-3.716660
-3.054627
-1.382529
-0.364473
X
E = -1035.08485
DG = -1013.82566
S9
0.000000
-0.599740
0.500727
1.547395
1.512587
0.417755
-0.639082
0.587909
1.710711
0.109751
0.159028
-0.702062
-0.742134
0.094111
0.955387
0.986148
-0.392723
-1.348588
-1.427035
0.071713
1.610953
1.642571
2.387773
2.346098
0.386152
-1.508230
-1.442633
-0.896751
-2.083370
-0.502663
-0.648387
0.357357
0.619015
-0.135171
-1.159678
-1.413413
0.943411
1.408222
0.062048
-1.765076
-2.206179
C
C
C
C
C
C
C
O
C
C
O
C
C
C
C
C
C
O
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
2.303724
1.253334
1.488734
2.736318
3.779989
3.553127
-0.089732
-0.368410
-0.193268
-1.502770
-1.590331
1.011402
1.244327
2.404553
3.365182
3.140868
1.973112
-0.370963
-2.786662
-3.765680
-4.983216
-5.250771
-4.290423
-3.065211
-3.554403
-5.724815
-6.204899
-4.498866
-2.304738
1.781582
3.876125
4.271021
2.562926
0.513855
-0.834119
0.674257
2.893032
4.754140
4.355820
2.115087
1.216051
1.507293
2.455525
3.061354
2.740829
1.817443
0.800764
0.334459
-0.346871
-1.102323
-2.332624
-1.271120
-2.008969
-2.763948
-2.804735
-2.086556
-1.336775
0.090793
-0.330520
-0.868392
-0.221348
0.970036
1.504858
0.864798
-1.800594
-0.647084
1.474681
2.426417
1.249474
-0.772132
-2.112912
-3.396166
-3.326216
-1.949773
1.548306
2.711567
3.793742
3.214095
1.568639
0.492564
C -0.225832 -0.472496 0.710539
O -0.526953 -0.400232 2.015942
C -0.118892 0.880865 -0.125837
O -0.693851 0.386892 -1.295902
C 1.212987 1.540590 -0.261260
C 2.033145 1.362836 -1.380942
C 3.302235 1.935710 -1.440047
C 3.782563 2.700399 -0.376401
C 2.969739 2.898544 0.740424
C 1.697820 2.333442 0.789162
C 1.055785 -1.288729 0.442623
C 1.467705 -1.751924 -0.816537
C 2.682696 -2.413317 -0.985125
C 3.532838 -2.627935 0.100464
C 3.139757 -2.178138 1.359126
C 1.915279 -1.527635 1.519379
H -3.446354 -1.139331 -1.917070
H -5.729555 -0.175608 -1.766361
H -6.363892 1.213731 0.203610
H -4.687470 1.627856 1.992406
H -2.385292 0.652298 1.803354
H 1.588470 -1.181373 2.498356
H 3.785806 -2.337641 2.221928
H 4.483652 -3.141174 -0.033743
H 2.971440 -2.761942 -1.976505
H 0.823470 -1.577570 -1.671684
H -0.782334 1.594960 0.412731
H 1.060062 2.506508 1.657068
H 3.324901 3.504812 1.572119
H 4.773821 3.146777 -0.422491
H 3.921945 1.784841 -2.322723
H 1.658421 0.758532 -2.204041
-1.318569
-0.441406
0.562075
0.711110
-0.157186
-1.179561
-0.570382
-1.811115
0.546451
0.307175
0.365297
0.374325
-0.794972
-0.951032
0.061638
1.234885
1.384916
1.828838
0.160847
-0.683755
-0.873384
-0.199545
0.657532
0.834013
-1.204417
-1.546317
-0.337654
1.198168
1.508566
2.296019
2.038473
-0.060481
-1.870882
-1.597171
-0.190406
1.239092
1.502131
-0.047235
-1.873125
-2.109964
XI
E = -1035.07839
DG = -1034.81772
C
C
C
C
C
C
C
O
O
C
C
C
C
C
C
C
C
TS X-XI
E = -1035.07345
DG = -1034.81165
C
C
C
C
C
C
C
O
-3.129480 0.499457 1.023593
-2.759025 -0.282798 -0.076843
-3.724062 -0.519869 -1.065886
-5.004074 0.016238 -0.976948
-5.361245 0.797312 0.124532
-4.418640 1.030070 1.122095
-1.380367 -0.913345 -0.288743
-1.407033 -2.060578 -0.828936
S10
3.234946
2.749166
3.621635
4.927775
5.403917
4.550647
1.351486
1.414409
0.630445
0.039100
0.317091
-0.938234
-1.342764
-1.889748
-3.213586
-4.017452
-3.477530
-1.226172
0.068494
1.017937
0.687357
-0.610077
-1.564035
0.524548
1.518730
-0.729824
-0.997726
0.477228
1.323846
-1.539532
-2.050639
-2.474791
-2.418557
-1.933457
-0.463869
-0.274601
0.274345
0.619896
0.411486
-0.134595
-0.714200
-1.553706
-1.269131
-0.015802
0.535390
0.280667
-0.043793
1.142234
1.199261
0.059704
-1.131557
C
O
H
H
H
H
H
H
H
H
H
H
H
C
C
C
C
C
H
H
H
H
H
-2.155887
0.783452
0.671263
-1.737726
-4.092808
-5.050711
-3.619021
-1.261758
3.261889
5.583567
6.428565
4.907891
2.567364
-1.732623
-2.941586
-3.382273
-2.596693
-1.398815
-1.367834
-3.538795
-4.320776
-2.922894
-0.786092
-1.494462
0.586777
-1.660827
-1.099222
-1.894074
-2.757010
-2.859013
-2.101626
2.034882
1.443693
-0.869052
-2.578318
-1.972016
1.660798
2.340563
2.726718
2.415778
1.716351
1.369075
2.574973
3.265654
2.717429
1.478968
-1.181056
1.781808
0.610571
-2.104008
-2.029037
0.098194
2.133756
2.032688
0.424671
1.048981
0.671672
-0.308329
-0.891056
1.383344
1.241624
-0.024069
-1.133714
-0.985195
2.366782
2.122357
-0.143323
-2.128891
-1.849790
C
C
C
C
C
H
H
H
H
H
C
C
C
C
C
H
H
H
H
H
4.192712
5.237084
5.013308
3.683537
2.622644
4.384289
6.255112
5.841431
3.484509
1.608006
-1.702965
-1.956766
-1.317954
-0.423728
-0.172696
-2.200121
-2.651250
-1.510558
0.087119
0.537981
0.196918
-0.476930
-1.624276
-2.068724
-1.410456
1.081047
-0.112945
-2.150617
-2.953237
-1.780067
2.787777
3.723499
3.620635
2.575988
1.637245
2.872622
4.539887
4.353588
2.490328
0.830845
-0.625152
-0.025891
0.766530
0.931722
0.341563
-1.231226
-0.169212
1.236215
1.537888
0.480930
-0.261151
0.73662
1.973677
2.194440
1.193662
-1.227414
0.548027
2.754054
3.151754
1.368711
3ag
E = -1035.07860
DG = -1034.82244
C
O
C
C
C
C
H
O
C
C
C
C
C
C
H
H
H
H
H
O
S11
1.783794
0.531324
2.833259
-0.600803
-1.857521
-0.815273
-0.439389
-2.562797
-2.268742
-1.546020
-2.014726
-3.219242
-3.941063
-3.488125
-0.599549
-1.430544
-3.578349
-4.876666
-4.062718
1.894773
0.476576
-0.107788
-0.239188
0.715899
-0.119921
1.726743
1.271166
0.229795
-1.160389
-1.568935
-2.575075
-3.247941
-2.871784
-1.864657
-1.088920
-2.851043
-4.039336
-3.379089
-1.583890
1.515697
-1.095854
-0.901044
-0.464833
-1.152777
-1.403326
-0.044554
-2.086357
-2.416952
-0.509269
0.656454
1.482849
1.209687
0.065627
-0.768549
0.889881
2.361130
1.864204
-0.171895
-1.648680
-1.790361
Structures of Figure 7
E = -1242.08945
DG = -1242.86994
1a
C
C
C
C
C
C
C
O
C
O
C
C
C
C
C
C
C
S
C
O
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
E = -689.52009
DG = -689.36163
C
O
C
C
C
C
C
C
H
H
H
H
H
C
O
C
C
C
C
C
C
H
H
H
H
H
-0.869134
-0.178820
-1.618840
-1.501431
-2.224561
-3.073952
-3.200343
-2.472546
-0.838599
-2.132421
-3.641289
-3.863429
-2.571684
-0.863178
-0.161403
-1.616251
-1.488841
-2.214769
-3.076894
-3.213232
-2.482708
-0.816132
-2.114918
-3.646402
-3.886200
-2.589670
-0.494387
-1.497332
-0.140468
-0.953149
-0.652129
0.456405
1.264835
0.969758
-1.814192
-1.278383
0.690533
2.125341
1.606113
0.480174
1.475086
0.134938
0.946211
0.653563
-0.445089
-1.252009
-0.965357
1.799544
1.278714
-0.672649
-2.104801
-1.600527
0.135581
0.254307
-1.078278
-2.213748
-3.358148
-3.373052
-2.245204
-1.098126
-2.178853
-4.241388
-4.270453
-2.260632
-0.220787
1.314430
1.195310
2.528705
3.664103
4.808904
4.824285
3.696514
2.549033
3.628837
5.692088
5.722001
3.712314
1.671753
A
2.644689
1.794993
2.367569
3.740083
4.571775
4.016091
0.322696
-0.032105
-0.688136
-0.430573
-2.139565
-3.053981
-4.415342
-4.884951
-3.983132
-2.621969
0.112421
0.729345
1.168002
-0.480674
2.199400
4.651629
5.642917
4.161323
1.728688
-2.680270
-5.107735
-5.947354
-4.344554
-1.932847
0.873773
-0.826885
1.518612
1.962122
0.271013
-0.647187
-0.918882
-1.428634
-1.653789
-1.373864
-0.865726
-0.649020
-0.293977
-1.056588
-1.798205
-0.788905
-1.770931
-1.634402
-0.499991
0.491444
0.349753
0.952797
2.323520
3.462675
2.984718
-0.255891
-0.639581
-1.550297
-2.052189
-1.657067
-2.651399
-2.414081
-0.384279
1.386570
1.137777
0.645531
1.255372
4.397156
3.014774
3.638495
1.413212
0.332925
-0.842519
-0.924062
0.158191
1.330599
0.560537
1.704732
-0.464783
-1.434276
-0.145262
-0.540634
-0.277942
0.378501
0.766077
0.512766
-0.991629
-0.033139
-1.384834
0.638416
2.324560
2.184323
0.088138
-1.844968
-1.688543
-1.058205
-0.588501
0.582490
1.268488
0.807681
-1.716114
-1.473480
-0.936365
-1.989370
-1.987745
E = -552.55401
DG = -552.51673
I(A)
S -0.116880
O 0.153199
C 1.306603
C -1.379005
H 1.320864
H 2.220072
H 1.209585
H -2.346180
H -1.325445
0.155787 -0.414269
1.497517 0.355873
-0.836120 0.126744
-0.831504 0.192787
-1.793470 -0.399757
-0.272396 -0.082114
-0.998461 1.207457
-0.443998 -0.146471
-0.958661 1.285016
E = -1242.12891
DG = -1242.90585
C 0.615146
C 0.185170
C 0.482167
C 1.196475
C 1.628347
C 1.336109
C -0.631713
O -0.712369
TS reactants- I(A)
S12
-1.685936 1.316199
-1.468723 0.003472
-2.425119 -0.965791
-3.575533 -0.634699
-3.781022 0.674742
-2.829367 1.651893
-0.222743 -0.375554
0.048520 -1.699873
C
O
C
C
C
C
C
C
C
S
O
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
-0.022443
-0.715892
1.407096
2.155125
3.496318
4.110819
3.375328
2.031215
-2.026399
-3.210737
-4.253739
-4.030441
0.155490
1.421994
2.193004
1.673107
0.395180
1.448814
3.849829
5.161381
4.065909
1.655975
-2.442355
-2.025675
-4.855601
-4.413192
-3.305978
1.042699
1.814635
1.383596
0.796541
1.125174
2.032711
2.618838
2.298203
-0.456929
0.825724
0.090731
1.085728
-2.235080
-4.313151
-4.674330
-2.977594
-0.945446
2.747549
3.324308
2.282788
0.673015
0.109392
-1.388701
-0.499144
1.783120
0.127899
1.513985
H
H
H
H
H
H
H
H
H
H
H
H
H
0.253039
0.916345
-0.018653
-1.047829
-1.214047
-0.350943
0.677376
0.838218
0.243863
-0.326513
-1.178328
1.273172
-1.987022
-1.402772
0.932742
2.675908
2.088062
1.639229
1.355567
-0.481196
-2.022811
-1.726274
-0.160837
1.339827
1.109022
1.641015
1.971862
IIA
E = -1242.11658
DG = -1242.89346
C
C
C
C
C
C
C
H
H
H
H
H
O
C
O
C
C
C
C
C
C
H
H
H
H
H
C
H
H
S
O
C
H
H
H
TS1(A)
E = -1242.11413
DG = -1242.89217
C
C
C
C
C
C
C
C
S
C
C
C
C
C
C
C
C
O
O
O
H
H
-0.561823
-0.285027
-0.877561
-1.734224
-2.013589
-1.425587
0.656397
2.087436
3.415089
3.057120
0.272439
-1.184002
-2.223000
-3.548187
-3.855605
-2.824963
-1.500472
1.118665
0.436508
4.664337
-0.691572
-3.052862
1.514487
1.393466
2.283366
3.282392
3.392521
2.502285
0.320222
0.750189
-0.506904
-0.934332
-1.115378
-1.423716
-0.965519
-1.264948
-2.017099
-2.480060
-2.191175
-2.043667
-0.139438
0.382934
-2.554117
-3.069151
-4.891373 -2.244015 0.560952
-4.346184 -0.908318 -1.463366
-1.977288 -0.373000 -2.002300
-0.675170 2.170123 -2.092914
-2.190146 3.973471 -1.274031
-2.689280 4.165393 1.152287
-1.643614 2.578017 2.756074
-0.103940 0.813042 1.929991
2.441135 1.347530 -1.185356
2.168516 1.373503 0.567825
3.804486 -1.664937 1.914960
3.159402 -0.014508 2.181292
2.054257 -1.361398 1.668367
1.229301
-0.135585
-1.029040
-0.567858
0.792841
1.692916
-0.624825
-0.333207
-0.134205
1.595355
-0.523930
-0.311101
-1.124820
-0.815111
0.317916
1.133938
0.814954
-0.383151
-1.927755
-0.027143
1.447488
2.019928
S13
0.250752
-1.179910
-1.449430
-2.743921
-3.790660
-3.529821
-2.232881
-0.627896
-2.938929
-4.802972
-4.340450
-2.027995
1.102917
0.666251
0.337032
-0.257847
-1.162999
-2.021483
-1.994241
-1.099640
-0.239077
-1.192720
-2.717453
-2.666544
-1.075153
0.451396
2.123395
2.295494
2.478287
3.393192
4.655066
2.922068
3.633984
3.007324
1.909101
-1.130025
-1.412031
-1.765616
-2.073502
-2.046761
-1.701177
-1.377859
-1.795785
-2.337015
-2.292848
-1.678207
-1.088971
-2.080451
0.332332
-0.328362
1.437466
1.986695
3.015263
3.502831
2.953674
1.931971
1.591441
3.435761
4.302770
3.319901
1.502330
0.706271
1.474378
1.111874
-0.571899
0.302283
-0.838350
-1.550296
0.125636
-1.245421
-0.597927
-0.209817
1.115762
1.522659
0.599769
-0.724335
-1.123741
1.831638
2.560318
0.912843
-1.450110
-2.152498
-0.415757
-0.630175
-1.848655
-0.228936
-1.138900
-0.753634
0.550906
1.470043
1.081368
-2.151929
-1.476788
0.852433
2.494132
1.808680
-0.508842
0.256527
-1.466760
-0.116366
-0.013655
1.616053
2.041374
2.129638
1.655377
O
O
C
C
S
O
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
TS2(A)
E = -1242.09899
DG = -1242.87697
C
C
C
C
C
C
C
C
S
C
O
C
O
C
C
C
C
C
C
O
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
1.369350
0.128337
-0.361115
0.345983
1.577423
2.071579
-0.605704
-2.084082
-2.928516
-2.328477
-0.018974
-0.016592
-0.847302
1.161000
2.432143
3.521286
3.354536
2.090404
1.007800
-4.407930
0.021081
1.952960
4.204430
4.505881
2.572401
1.762025
3.018573
2.131132
-0.072762
-1.314035
-2.545721
-2.506090
-2.693153
-2.736938
-1.233091
2.012493
1.629239
2.454163
3.559466
3.906901
3.120957
0.487481
0.456151
-0.803342
-0.168042
-0.164377
-1.331540
-2.218374
-1.584918
-1.082415
-1.402183
-2.225562
-2.745401
-2.438593
-0.399949
-2.847139
-3.395245
-2.469900
-1.008960
-0.457810
1.439854
3.378727
4.770560
4.159335
2.223471
1.399342
0.190955
-0.836989
0.838522
-0.158808
0.930659
0.365823
-0.678466
-1.131181
-0.570104
0.470954
0.852943
0.830288
-0.289288
-1.874071
1.996219
1.262107
1.494011
0.390149
0.684010
-0.125639
-1.235627
-1.524805
-0.710949
-0.232925
-0.922687
-2.386258
-1.868674
0.118286
1.560957
1.765295
0.943535
-0.930582
-1.937880
-1.148294
0.500075
1.808165
-2.657430
-2.021383
-1.869513
2.039295
0.145416
0.595787
0.881390
-0.671859
-0.160471
0.326351
-0.154871
-0.368628
-0.123295
0.346311
0.559004
-1.343486
-0.349439
-0.736046
-0.291835
0.548603
0.925354
-1.535200
-2.546425
-1.326939
0.913576
1.925555
1.327004
1.490363
-2.287734
-1.511118
-0.620656
DMF
E = -248.37578
DG = -248.303206
C -0.088010 0.178702 0.076812
O -0.086063 0.018952 1.295257
H 0.645549 0.834461 -0.429528
N -0.943573 -0.393269 -0.792522
C -0.863202 -0.140987 -2.216512
C -1.988168 -1.292837 -0.346679
H -1.797938 0.303010 -2.579844
H -0.041294 0.548488 -2.427092
H -0.687140 -1.076404 -2.761429
H -2.972151 -0.897994 -0.627153
H -1.862917 -2.277479 -0.813081
H -1.935625 -1.396828 0.738180
E = -1242.11389
DG = -1242.89445
3.926028
2.744429
2.815243
4.052038
5.226591
5.161244
1.448622
0.663620
-0.122681
0.071271
1.440910
2.597347
4.012646
-1.023548
-2.273273
-3.362169
-3.296588
-2.081261
-0.979531
1.962315
-2.370789
-4.290467
-4.155257
-1.989709
-0.059582
-0.970994
-1.494939
-0.944478
0.123617
0.635152
1.551440
1.993007
2.473454
0.884784
2.167248
Other Structures
III(A)
C
C
C
C
C
C
C
1.363121
0.410714
-0.930622
-1.296821
-1.363978
-1.687801
-1.779925
-1.278041
-2.110941
-3.486388
-4.002652
-3.191091
-2.920352
-0.211621
-1.672543
-4.131815
-5.069931
-3.645565
1.898862
4.100759
6.192296
6.074909
3.859206
-2.293104
-0.569334
-3.123992
-2.818354
-3.718565
0.170508 0.945040
-0.132678 0.261216
-0.733918 -1.001352
-1.026564 -1.566366
-0.718456 -0.880934
-0.118778 0.376240
0.178641 0.919388
S14
C (Scheme 1)
F (Scheme 5)
E = -247.83143
DG = -247.77322
E = -247.71468
DG = -247.65524
C 0.020165 0.072202 -0.068182
N 0.116198 0.348413 1.338567
C 1.420347 0.120210 1.924323
C -1.006929 0.805351 2.052647
O -0.809993 1.015696 3.282488
H 0.256232 -0.980385 -0.297585
H -1.006432 0.280059 -0.393927
H 0.710442 0.698054 -0.658206
H 1.735264 -0.929292 1.811656
H 2.190795 0.749781 1.451685
H 1.362098 0.364484 2.989994
247.714678
C -0.000105 0.079460 -0.077170
N 0.139157 0.343197 1.344975
C 1.456573 0.109132 1.935481
C -0.886069 0.776118 2.064813
O -0.976853 1.050810 3.240578
H 0.228418 -0.971222 -0.290270
H -1.026076 0.295015 -0.383540
H 0.688932 0.712877 -0.647802
H 1.741332 -0.940616 1.802422
H 2.201685 0.744469 1.443672
H 1.421192 0.345334 3.000300
V (Scheme 5)
E = -689.63884
DG = -689.48333
C
O
C
C
C
C
C
C
H
H
H
H
H
C
O
C
C
C
C
C
C
H
H
H
H
H
-1.937592
-1.812954
-2.056161
-1.718255
-1.845261
-2.331249
-2.685489
-2.545950
-1.353347
-1.566221
-2.435107
-3.075239
-2.814318
-1.931763
-1.792794
-2.055095
-1.706194
-1.836351
-2.336604
-2.701833
-2.559205
-1.330126
-1.548596
-2.442969
-3.102715
-2.836260
-0.477647
-1.725659
0.002122
-0.903956
-0.566659
0.689209
1.596024
1.263842
-1.886503
-1.287015
0.956761
2.575631
1.981640
0.475771
1.722257
-0.002595
0.899525
0.563721
-0.686453
-1.589121
-1.258576
1.877793
1.280810
-0.952784
-2.564164
-1.973231
0.173333
0.364292
-1.235804
-2.256781
-3.599303
-3.963280
-2.964648
-1.619818
-1.966991
-4.366140
-5.012686
-3.235759
-0.851438
1.277266
1.086230
2.686472
3.707255
5.049850
5.414105
4.415674
3.070765
3.417256
5.816527
6.463569
4.687007
2.302538
S15
1
H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 3ba
Cl
Cl
O
O
O
Cl
3ba
S16
1
H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 6
OH
N
Ph
O
6
S17
1
H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 7
Ph
O
O
N
Ph
7 O
S18
1
H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 8
Cl
OH
O
Ph
OH
N
8
S19
1
H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 12
OH
Ph
N
Ph
O
12
S20
1
H (300 MHz) and 13C (75 MHz) spectra (CDCl3) of 13
OAc
OAc
Ph
Ph
13
S21
References
1.
Y. Zhao, N. E. Schultz and D. G. Truhlar, J. Chem. Theory Comput., 2006, 2, 364-382.
2.
Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M.
A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H.
Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L.
Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F.
Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi,
J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi,
N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J.
Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J.
W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J.
Dannenberg, S. Dapprich, A. D. Daniels, . Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski
and D. J. Fox, Gaussian, Inc., Wallingford CT, 2009.
3.
J. Tomasi, B. Mennucci and R. Cammi, Chem. Rev., 2005, 105, 2999-3093.
S22