Rotational energy barrier around the C1-C11 single bond in lamellarins: A study by variable-temperature NMR

Article abstract of DOI:10.3987/COM-13-S(S)69

In order to estimate the free energy barrier to rotation around the C1-C11 single bond in lamellarins, new lamellarin analogues (1a), (1b), (2a), and (2b) possessing diastereotopic protons or carbons at the C1 aryl moiety were synthesized. Variable-temperature ¹H and ¹³C NMR measurements of these analogues revealed that the free energy barriers to rotation around the C1-C11 axis in 5,6-saturated and 5,6-unsaturated lamellarins were around 72-74 and 83-87 kJ/mol, respectively.

Full text of DOI:10.3987/COM-13-S(S)69

Supporting information
Rotational Energy Barrier Around the C1–C11 Single Bond in Lamellarins:
a Study by Variable-Temperature NMR
Tsutomu Fukuda, Ryosuke Itoyama, Terufusa Minagawa, and Masatomo Iwao
Division of Chemistry and Materials Science, Graduate School of Engineering, Nagasaki University,
1-14 Bunkyo-machi, Nagasaki 852-8521, Japan
List of Contents
1H and 13C spectra
Theoretical calculations
References
S2–S11
S12–S21
S22
-S1-

MeO
Oi-Pr
Br
O
MeO
N
O
i-PrO
4
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S1. H NMR spectrum of compound (4) (400 MHz, CDCl3).
200
180
160
140
120
100
80
60
40
20
0
/ppm(13C)
ꢀ
Figure S2. 13C NMR spectrum of compound (4) (100 MHz, CDCl3).
-S2-

O
O
Br
5b'
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S3. H NMR spectrum of compound (5b') (400 MHz, CDCl3).
160
140
120
100
80
60
40
20
0
/ppm(13C)
ꢀ
Figure S4. 13C NMR spectrum of compound (5b') (100 MHz, CDCl3).
-S3-

O
O
B(OH)2
5b
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S5. H NMR spectrum of compound (5b) (400 MHz, CDCl3).
160
140
120
100
80
60
40
20
0
/ppm(13C)
ꢀ
Figure S6. 13C NMR spectrum of compound (5b) (100 MHz, CDCl3).
-S4-

MeO
O
Oi-Pr
O
O
MeO
N
O
i-PrO
1a
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S7. H NMR spectrum of compound (1a) (400 MHz, CDCl3).
160
140
120
100
80
60
40
20
0
/ppm(13C)
ꢀ
Figure S8. 13C NMR spectrum of compound (1a) (100 MHz, CDCl3).
-S5-

MeO
O
Oi-Pr
O
O
MeO
N
O
i-PrO
1b
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S9. H NMR spectrum of compound (1b) (400 MHz, CDCl3).
160
140
120
100
80
60
40
20
0
/ppm(13C)
ꢀ
Figure S10. 13C NMR spectrum of compound (1b) (100 MHz, CDCl3).
-S6-

MeO
O
Oi-Pr
O
O
MeO
N
O
i-PrO
1b
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S11. H NMR spectrum of compound (1b) (400 MHz, toluene-d8).
160
140
120
100
80
60
40
20
0
/ppm(13C)
ꢀ
Figure S12. 13C NMR spectrum of compound (1b) (100 MHz, toluene-d8).
-S7-

MeO
O
Oi-Pr
O
O
MeO
N
O
i-PrO
2a
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S13. H NMR spectrum of compound (2a) (400 MHz, CDCl3).
160
140
120
100
80
60
40
20
0
/ppm(13C)
ꢀ
Figure S14. 13C NMR spectrum of compound (2a) (100 MHz, CDCl3).
-S8-

MeO
O
Oi-Pr
O
O
MeO
N
O
i-PrO
2a
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S15. H NMR spectrum of compound (2a) (400 MHz, toluene-d8).
-S9-

MeO
O
Oi-Pr
O
O
MeO
N
O
i-PrO
2b
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S16. H NMR spectrum of compound (2b) (400 MHz, CDCl3).
160
140
120
100
80
60
40
20
0
/ppm(13C)
ꢀ
Figure S17. 13C NMR spectrum of compound (2b) (100 MHz, CDCl3).
-S10-

MeO
O
Oi-Pr
O
O
MeO
N
O
i-PrO
2b
9
8
7
6
5
4
3
2
1
0
/ppm(1H)
ꢀ
1
Figure S18. H NMR spectrum of compound (2b) (400 MHz, toluene-d8).
160
140
120
100
80
60
40
20
0
/ppm(13C)
ꢀ
Figure S19. 13C NMR spectrum of compound (2b) (100 MHz, toluene-d8).
-S11-

Theoretical calculations
All calculations were performed with Spartan ’10 for Windows program package.1 Equilibrium
and transition state structures involved in the enantiomerization process of 1a and 2a were
optimized using B3LYP DFT theory level2 with the 6-31G(d) basis set. The nature of the obtained
stationary points (minimum or first order saddle point) was confirmed through analysis of
vibrational frequencies. Thermodynamic properties (enthalpies, Gibbs free energies, and entropies)
were computed for a standard pressure of 0.1 MPa (1 atm) and for the coalescence temperatures Tc
as determined in the VT-NMR experiment and a temperature of 20 °C (293 K). For the calculation
of the partition functions, the vibrational frequencies were scaled by a factor of 0.9806.3
1a-TS1
φ = –4.96°
ΔG = 69.69 kJ/mol (323 K)
69.38 kJ/mol (293 K)
MeO
O
Oi-Pr
O
11
12
1
φ
O
MeO
10b
N
O
i-PrO
1a
(aR)-1a
φ = –76.69°
(aS)-1a
φ = 106.70°
ΔG = 0.00 kJ/mol (323 K)
0.00 kJ/mol (293 K)
ΔG = 0.26 kJ/mol (323 K)
0.17 kJ/mol (293 K)
1a-TS2
φ = 178.08°
ΔG = 71.59 kJ/mol (323 K)
71.44 kJ/mol (293 K)
Figure S20. DFT-optimized structures for the ground states and transition states of the enantiomerization of
5,6-saturated lamellarin analogue (1a)
Table S1. Calculated enthalpies (ΔH), entropy contributions (–TΔS), and Gibbs free energies (ΔG) for ground state
and transition state structures of 5,6-saturated lamellarin analogue (1a)a
Tc (323 K)
–TΔS
0.00
–0.14
0.02
–0.20
20 °C (293 K)
–TΔS
0.00
φb
species
ΔH
0.00
69.83
0.24
71.79
ΔG
0.00
69.69
0.26
71.59
ΔH
0.00
69.83
0.24
71.79
ΔG
0.00
69.38
0.17
71.44
(aR)-1a
1a-TS1
(aS)-1a
1a-TS2
–76.69
–4.96
106.70
178.08
–0.45
–0.07
–0.35
a Values for enthalpies (ΔH), entropy contributions (–TΔS), and Gibbs free energies (ΔG) were given in kJ/mol.
b Values for torsion angle C10b–C1–C11–C12 was given in degree (°).
-S12-

2a-TS1
φ = 13.03°
ΔG = 82.02 kJ/mol (368 K)
82.02 kJ/mol (293 K)
MeO
O
Oi-Pr
O
11
12
1
φ
O
MeO
10b
N
O
i-PrO
2a
(aR)-2a
(aS)-2a
φ = –89.26°
φ = 89.26°
ΔG = 0.00 kJ/mol (368 K)
0.00 kJ/mol (293 K)
ΔG = 0.00 kJ/mol (368 K)
0.00 kJ/mol (293 K)
2a-TS2
φ = 192.06°
ΔG = 90.06 kJ/mol (368 K)
89.79 kJ/mol (293 K)
Figure S21. DFT-optimized structures for the ground states and transition states of the enantiomerization of
5,6-unsaturated lamellarin analogue (2a)
Table S2. Calculated enthalpies (ΔH), entropy contributions (–TΔS), and Gibbs free energies (ΔG) for ground state
and transition state structures of 5,6-unsaturated lamellarin analogue (2a)a
Tc (368 K)
–TΔS
0.00
–0.22
0.00
–0.38
20 °C (293 K)
–TΔS
0.00
φb
species
ΔH
0.00
82.24
0.00
90.44
ΔG
0.00
82.02
0.00
90.06
ΔH
0.00
82.32
0.00
90.57
ΔG
0.00
82.02
0.00
89.79
(aR)-2a
2a-TS1
(aS)-2a
2a-TS2
–89.26
13.03
89.26
–0.30
0.00
–0.78
192.06
a Values for enthalpies (ΔH), entropy contributions (–TΔS), and Gibbs free energies (ΔG) were given in kJ/mol.
b Values for torsion angle C10b–C1–C11–C12 was given in degree (°).
-S13-

Cartesian coordinates (in Å, 1 Å = 100 pm) of the DFT-optimized geometry of (aR)-1a.
N
C
C
C
C
C
C
C
C
C
C
H
H
C
C
C
C
C
C
H
H
H
C
C
C
C
C
C
H
H
O
C
O
O
O
O
O
O
O
C
H
H
H
C
H
H
H
C
H
H
C
H
C
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
C
H
H
0.644411
-0.722054
1.108887
-1.148525
0.012719
-2.571087
-5.379751
-3.176575
-3.407030
-4.793476
-4.554199
-2.541618
-5.418383
0.054570
0.115666
-0.065025
0.207964
0.236389
-0.039526
-0.180470
0.295412
-0.136092
2.553462
5.338591
3.356728
3.156172
4.529642
4.734409
2.536752
5.375812
-2.928547
-1.589606
-1.280560
-6.731827
-5.204661
6.682261
5.178618
0.145087
0.342260
-4.421661
-3.710843
-3.867588
-5.127828
4.403675
3.902878
5.108712
3.648824
0.467428
-0.233557
1.502354
-7.517724
-6.959895
7.532666
7.040134
7.756858
6.806482
8.256184
8.384124
8.817790
8.603841
9.522430
9.294321
-8.794957
-9.450659
-9.337211
-8.557516
-7.769764
-8.348092
-6.826314
-8.330800
1.535342
1.902774
0.948818
2.701015
3.425638
2.325361
-2.555420
-2.547751
-1.260964
-1.220952
-0.396769
-0.968002
-0.716448
0.302364
-2.097456
-1.970828
0.439270
1.176753
-2.856427
1.089204
3.864458
1.770115
1.823965
3.200644
3.175474
1.192455
1.320396
3.695636
-1.034832
-0.677630
-2.071184
0.172314
0.366030
-1.872309
0.957047
-2.654437
-3.385579
-3.696933
-4.868263
-0.624992
1.635960
-0.516497
1.520898
5.222974
4.120640
2.818962
2.817191
2.953661
3.641840
2.607023
2.357669
3.423085
2.920818
5.393324
6.100428
5.752067
-0.023089
0.828359
-0.360666
0.323044
-1.715041
-2.162661
-2.406211
-1.601603
0.274592
1.239665
0.432216
-0.373392
0.475355
0.948329
-0.358178
1.205916
-1.049807
-0.601880
-1.418697
-1.904955
-3.715567
-3.961782
-4.559172
-3.363863
-4.185131
-3.273263
0.123483
-0.026826
0.075293
-0.150910
-0.089741
-0.272466
-0.492730
-0.372564
-0.286256
-0.393193
-0.490162
-0.367752
-0.406021
-0.134612
-0.246907
-1.355477
1.065799
0.972901
-1.433994
-2.267459
2.021991
-2.381069
0.188362
0.423756
0.704608
-0.212091
-0.084976
0.808422
-0.622475
1.205025
-0.183120
-0.024828
0.094334
-0.677991
-0.618278
0.626070
-0.422089
-0.040237
1.989084
-0.639006
-1.475429
0.299442
-0.764662
-0.907154
-1.851785
-1.075908
-0.174939
1.346068
1.798016
1.439500
0.386440
0.790043
-0.542373
-1.241261
-1.210966
-1.520608
-0.522349
-2.102865
-0.030764
0.438135
-0.854649
0.713393
-0.274506
0.464878
-0.734967
-1.053438
1.488197
2.304889
1.904411
1.094740
0.215405
-0.790121
0.576473
1.138370
1.135181
2.168369
-S14-

Cartesian coordinates (in Å, 1 Å = 100 pm) of the DFT-optimized geometry of 1a-TS1.
N
C
C
C
C
C
C
C
C
C
C
H
H
C
C
C
C
C
C
H
H
H
C
C
C
C
C
C
H
H
O
C
O
O
O
O
O
O
O
C
H
H
H
C
H
H
H
C
H
H
C
H
C
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
C
H
H
0.445260
-0.921180
0.985814
-1.278790
-0.058774
-2.695292
-5.496173
-3.250533
-3.586758
-4.962280
-4.612588
-2.612695
-5.614084
0.123076
0.449013
-0.950660
1.395175
1.520334
-0.811333
-1.951635
2.254326
-1.669828
2.424143
5.165515
3.242703
2.976553
4.330151
4.600515
2.325646
5.252139
-3.163202
-1.835277
-1.565818
-6.845698
-5.075862
6.484502
4.931779
0.873459
2.661945
-5.500477
-5.856758
-6.308772
-4.659879
4.133458
4.810406
3.686083
3.337508
2.219240
2.243062
2.859260
-7.585218
-7.042500
7.383436
6.874665
8.581653
8.263592
9.067788
9.315592
7.752495
6.859543
8.416356
8.267249
-8.934640
-8.810569
-9.558081
-9.459990
-7.706807
-8.246154
-8.254430
-6.721220
1.254461
1.414762
0.681804
2.592671
3.234311
2.415097
-2.383680
-2.283030
-1.147800
-0.956601
-0.184035
-0.736750
-0.579709
0.296539
-1.763076
-1.666694
0.387874
1.030111
-2.460157
1.276126
4.005274
2.186268
1.779430
3.120317
3.552972
1.835489
1.137087
4.215753
-1.118351
-1.207975
-2.134305
-0.193280
-0.222721
-2.153763
0.540621
-2.927219
-2.936533
-3.320115
-4.440557
-0.537703
1.444031
-1.323226
0.630519
5.275137
3.803998
1.081311
2.001329
0.343231
0.678588
1.634791
2.203757
2.303262
1.194962
5.116183
5.224919
5.861148
0.566844
1.494402
-0.250042
0.705379
-0.353645
-0.240396
-1.329582
0.426287
-0.398955
-0.369074
0.415486
-1.350926
0.584488
0.734747
1.394641
-0.364107
0.366595
-0.561035
1.202682
0.314888
-3.593753
-4.069222
-4.279723
-3.196474
-4.080031
-2.830486
0.582268
0.579761
0.314122
0.298540
0.264919
0.015530
-0.493834
-0.766973
0.399517
0.191069
-1.020965
-1.242857
0.538817
0.496967
1.118745
0.498118
0.896560
1.174464
0.797075
0.315070
1.013845
0.785444
0.008943
-0.639364
0.537252
-0.898341
-1.222083
0.212400
-1.355283
0.608997
0.977981
0.990484
1.380307
-0.729045
-1.778476
-0.979167
-2.102491
1.432753
1.537141
-3.097479
-3.566767
-3.066642
-3.677556
-2.713220
-3.352806
-1.966484
-3.327913
1.897446
2.991515
1.416737
-0.131677
-0.344294
-0.585316
-0.748412
-1.517859
-2.558475
-1.408522
-1.287090
0.888788
1.522297
1.201487
1.061701
-0.836020
-1.912982
-0.442694
-0.678989
1.376805
1.599595
1.826776
1.850574
0.766401
-0.210570
1.388836
1.391671
1.470875
2.413212
-S15-

Cartesian coordinates (in Å, 1 Å = 100 pm) of the DFT-optimized geometry of (aS)-1a.
N
C
C
C
C
C
C
C
C
C
C
H
H
C
C
C
C
C
C
H
H
H
C
C
C
C
C
C
H
H
O
C
O
O
O
O
O
O
O
C
H
H
H
C
H
H
H
C
H
H
C
H
C
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
C
H
H
0.711690
-0.662351
1.160575
-1.108478
0.047482
-2.538607
-5.359031
-3.162535
-3.362989
-4.754563
-4.546461
-2.538476
-5.370131
0.075911
0.141787
0.395945
-0.222534
-0.183108
0.437205
0.622074
-0.475199
0.680656
2.608260
5.400948
3.457353
3.169554
4.547046
4.837538
2.515578
5.513559
-2.866680
-1.516796
-1.188725
-6.722342
-5.215454
6.754151
5.159123
0.078186
-0.461929
-4.447462
-5.169188
-3.809940
-3.818460
4.339507
3.766392
5.023041
3.644851
-0.120437
0.809361
-0.940725
-7.431205
-6.874135
7.513253
6.948596
7.733895
6.778901
8.302881
8.292374
8.809214
8.596176
9.448671
9.358437
-7.541703
-8.058595
-8.104419
-6.550829
-8.782173
-9.388126
-8.646937
-9.327801
1.615265
1.902634
1.065483
2.848984
3.577596
2.557507
-2.575472
-2.573127
-1.278554
-1.250742
-0.420866
-1.012210
-0.789006
0.244838
-2.145212
-2.031819
0.367419
1.120145
-2.920054
1.057623
3.818204
1.643879
1.883481
3.250128
3.039230
0.998268
1.453822
3.484822
-1.043915
-0.671764
-2.127576
0.218127
0.417715
-1.919823
1.042077
-2.737818
-3.424843
-3.728297
-4.897953
-0.718364
1.549376
-0.514048
1.620704
5.188733
4.245608
2.727158
3.536277
2.939729
2.655890
2.753193
2.641074
3.598820
2.936051
5.471462
5.871322
6.185670
-0.042498
0.861448
-0.174494
0.569746
-1.424296
-1.868774
-2.174327
-1.175677
0.446344
1.336181
0.734196
-0.267855
-0.963857
-0.454529
-1.869125
-1.263519
0.347984
0.867206
1.008491
-0.543298
-3.719879
-3.813107
-4.617063
-3.481377
-4.279320
-3.547029
0.101931
0.061160
0.201401
0.160251
0.248097
0.191220
0.220155
0.336927
0.082866
0.089301
0.360069
0.446822
0.005073
0.397107
0.705132
1.629584
-0.715508
-0.525478
1.806664
2.472075
-1.678788
2.765192
0.230943
0.304487
0.531719
-0.040418
0.010243
0.558699
-0.287911
0.791779
-0.038746
-0.033759
-0.111417
0.305244
0.524173
0.429952
-0.206124
0.613598
-1.433521
0.713945
0.840758
-0.154585
1.610797
-0.454514
-1.384441
-0.550907
0.375061
-0.776467
-1.205844
-0.888944
-0.768549
-1.036110
-0.762160
-1.332823
-1.611200
-1.911203
-1.050004
-2.521287
-0.260505
0.339328
-1.102263
0.363197
-1.981123
-2.802963
-1.726279
-2.338462
-0.186170
-0.936889
0.675442
0.143233
-0.043880
-1.100041
0.236795
0.825514
0.646562
1.884307
-S16-

Cartesian coordinates (in Å, 1 Å = 100 pm) of the DFT-optimized geometry of 1a-TS2.
N
C
C
C
C
C
C
C
C
C
C
H
H
C
C
C
C
C
C
H
H
H
C
C
C
C
C
C
H
H
O
C
O
O
O
O
O
O
O
C
H
H
H
C
H
H
H
C
H
H
C
H
C
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
C
H
H
0.693668
-0.673614
1.202192
-1.064236
0.139472
-2.495295
-5.319693
-3.103980
-3.353005
-4.736497
-4.479517
-2.502946
-5.356731
0.302505
0.668803
1.555972
-0.803342
-0.585638
1.764936
2.405743
-1.812372
2.746137
2.627619
5.343729
3.483002
3.129705
4.469664
4.827953
2.450052
5.507345
-2.882911
-1.552245
-1.249151
-6.684389
-5.002267
6.649778
5.021713
0.585109
-1.516024
-5.531684
-5.935722
-6.329441
-4.741240
4.177617
4.817932
3.373756
3.736482
-0.818305
-1.138342
-1.016425
-7.275102
-6.710888
7.547924
7.018844
7.981523
7.115973
8.517210
8.646172
8.706905
8.343057
9.438636
9.211345
-8.700123
-9.220012
-9.255504
-8.704559
-7.213510
-7.642090
-6.180187
-7.778951
1.529102
0.993498
1.656184
2.885257
2.744233
3.543727
-2.316043
-2.237944
-1.078037
-0.924314
-0.133126
-0.733770
-0.640757
0.269038
-1.753732
-1.692684
0.339460
0.995477
-2.487468
1.334083
4.069507
1.873630
2.224293
3.556361
3.233993
1.217266
1.887389
3.603806
-1.029033
-1.081598
-2.023195
-0.105790
-0.117949
-2.024080
0.613724
-2.781042
-2.901703
-3.273338
-4.380526
-0.571770
1.349039
-1.182626
0.734145
5.426554
4.573695
2.447778
3.151501
2.118061
2.940854
1.703086
2.274248
1.228533
2.377407
5.718155
5.919858
6.578068
-0.754513
-0.143830
-0.088522
0.856035
-0.200372
-0.169699
-1.141112
0.629673
-0.195954
-0.110235
0.598859
-1.162519
-0.231478
-0.332926
-0.796877
0.824541
-2.224860
-2.360833
-2.585836
-2.843431
-3.510185
-4.193984
-3.999374
-3.082497
-2.703521
-3.954705
-0.750605
-0.802162
-0.436385
-0.505235
-0.407882
-0.279260
0.113327
0.501932
-0.748420
-0.587771
0.683093
1.033368
-0.986368
-0.607124
-1.178969
-0.971076
-0.607206
-0.880841
-1.245343
-1.084683
-0.447384
-1.523585
-0.077496
0.673571
-0.588322
0.860125
1.235998
-0.212360
1.297498
-0.593903
-1.343021
-1.288150
-1.690815
0.205800
1.466338
1.064083
2.149960
-1.385067
-0.896954
0.716357
1.447946
0.041083
0.135172
2.756317
3.430700
3.333649
2.010971
-1.399485
-2.431902
-0.753576
1.525826
2.238230
0.731626
0.893215
-0.728097
-1.398637
-0.898695
-0.994864
1.712198
2.740356
1.530274
1.602757
1.411957
2.370755
0.655375
1.124610
1.931593
2.931300
1.956539
1.225283
-0.920970
-1.577926
0.054102
-1.483742
-2.506266
-1.549500
-S17-

Cartesian coordinates (in Å, 1 Å = 100 pm) of the DFT-optimized geometry of (aR)-2a.
N
C
C
C
C
C
C
C
C
C
C
H
H
C
C
C
C
C
C
H
H
H
C
C
C
C
C
C
H
H
O
C
O
C
H
C
H
O
O
O
O
O
O
C
H
H
H
C
H
H
H
C
H
H
C
H
C
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
H
0.679671
-0.703064
1.160852
-1.111362
0.052594
-2.536086
-5.348090
-3.128489
-3.385708
-4.774241
-4.508391
-2.482097
-5.411752
0.088182
0.106890
0.076535
0.110354
0.118731
0.087453
0.055286
0.120344
0.080888
2.592334
5.408432
3.432040
3.186869
4.564442
4.831974
2.550103
5.489425
-2.922126
-1.575589
-1.270949
2.842849
3.483573
1.499575
0.976995
-6.708282
-5.149183
6.767807
5.207595
0.145864
0.166521
-4.353195
-3.713059
-5.055009
-3.722434
4.418441
5.127052
3.787922
3.781220
-0.001402
-1.007310
0.767894
-7.402816
-6.808395
7.462206
6.856329
8.769839
8.570190
9.361310
9.362125
7.660381
6.698819
8.166909
8.270028
-8.724530
-8.544758
-9.318359
-9.305104
-7.574138
-8.081192
-6.603476
-8.172349
-2.651010
-2.617129
-1.342157
-1.281339
-0.470526
-1.010969
-0.718617
0.266533
-2.128811
-1.980214
0.423619
1.129766
-2.855296
1.015139
3.788018
1.669257
1.776355
3.151607
3.073079
1.071317
1.292491
3.572564
-1.148808
-0.864178
-2.295026
0.130861
0.281906
-2.116376
0.999680
-2.979210
-3.423059
-3.752533
-4.929228
-3.602569
-4.476375
-3.765673
-4.710469
-0.611314
1.627253
-0.749903
1.478578
5.150326
4.093931
2.792319
2.957684
3.622621
2.738847
2.652946
3.477031
2.815381
2.608596
5.357375
5.748059
6.052186
0.039036
0.899169
-0.099330
0.746438
0.416115
1.123943
-0.413562
0.920326
-1.091705
-1.475477
-0.608490
-1.940478
0.524830
1.226310
1.027989
-0.319686
-0.942634
-0.457317
-1.306509
-1.805537
-0.143946
-0.145702
-0.223852
-0.226930
-0.276496
-0.242312
-0.254111
-0.328993
-0.172639
-0.173120
-0.345098
-0.397859
-0.121110
-0.349831
-0.514297
-1.590326
0.844830
0.726013
-1.695854
-2.496018
1.815222
-2.658771
-0.239151
-0.252665
-0.167908
-0.330375
-0.347140
-0.171454
-0.402914
-0.121408
-0.091844
-0.072411
0.003291
-0.086758
-0.034067
-0.076594
-0.019352
-0.336261
-0.457311
-0.337637
-0.463524
-0.336209
1.726565
-0.602959
0.274032
-0.701408
-1.499734
-0.595732
-0.694435
0.287852
-1.487722
1.074153
1.283728
1.421952
0.763206
1.088147
0.762260
1.103392
0.178777
-0.631084
-0.224435
0.950276
1.905514
2.262859
2.749192
1.575616
0.185796
-0.634257
0.956851
-0.202096
1.919981
2.762230
2.273282
1.606181
-S18-

Cartesian coordinates (in Å, 1 Å = 100 pm) of the DFT-optimized geometry of 2a-TS1.
N
C
C
C
C
C
C
C
C
C
C
H
H
C
C
C
C
C
C
H
H
H
C
C
C
C
C
C
H
H
O
C
O
C
H
C
H
O
O
O
O
O
O
C
H
H
H
C
H
H
H
C
H
H
C
H
C
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
H
0.527599
-0.849308
1.060259
-1.209549
-0.008085
-2.619007
-5.389617
-3.157360
-3.504543
-4.869566
-4.505628
-2.514144
-5.522769
0.080019
0.151569
-1.072675
1.318068
1.311622
-1.064370
-2.015914
2.265393
-1.978848
2.464967
5.228922
3.271166
3.044977
4.394121
4.650813
2.403755
5.283401
-3.090299
-1.753808
-1.479942
2.648735
3.255235
1.300189
0.739024
-6.724192
-4.965411
6.551069
5.008808
0.451692
2.394020
-5.283457
-4.388849
-5.648106
-6.058757
4.229633
4.920435
3.788390
3.432396
1.881978
2.204560
2.236626
-7.527135
-6.997183
7.435308
6.915150
8.639213
8.325199
9.136414
9.362150
7.797632
6.900676
8.445868
8.327347
-8.832157
-9.340251
-8.648080
-9.499199
-7.733344
-8.325302
-6.776772
-8.264518
-2.410033
-2.321551
-1.162040
-1.006473
-0.213638
-0.793924
-0.655448
0.290960
-1.852938
-1.770928
0.370157
1.090959
-2.592400
1.247925
3.976116
1.965952
1.945270
3.279600
3.326412
1.449657
1.457575
3.834043
-1.155974
-1.230004
-2.263084
-0.174879
-0.196139
-2.246731
0.570193
-3.070290
-3.036242
-3.380555
-4.497870
-3.413799
-4.261535
-3.499643
-4.363505
-0.627561
1.470917
-1.307058
0.699684
5.291086
4.131918
1.210145
0.892498
2.153450
0.441786
1.754235
2.350960
2.381085
1.366069
5.343753
5.424641
6.196470
0.416903
1.368312
-0.263771
0.696508
-0.265624
-0.058990
-1.241797
0.497735
-0.545601
-0.590791
0.246261
-1.501140
0.452147
-0.516581
0.678072
1.219410
0.108545
0.900791
0.041406
-0.841887
0.693612
0.679248
0.351773
0.367604
0.317529
0.053604
-0.575296
-0.668935
0.349551
0.072584
-0.984618
-1.014503
0.343997
0.582080
1.298091
0.968778
0.649252
0.986954
1.314775
1.058764
0.491107
1.602043
-0.000525
-0.639809
0.391593
-0.841130
-1.159604
0.094574
-1.290179
0.411930
0.912889
1.027068
1.424839
0.981339
1.281194
1.057520
1.385106
-0.881336
-1.677691
-0.970749
-1.981727
1.569035
1.059140
-3.049491
-3.600835
-3.462685
-3.139218
-2.532663
-3.130442
-1.747368
-3.179202
1.624526
2.672783
1.039212
-0.256868
-0.372537
-0.473987
-0.550750
-1.404789
-2.432179
-1.383885
-1.096977
0.982093
1.609028
1.375135
1.067997
-1.039897
-0.978444
-2.094785
-0.632361
1.223869
1.696434
1.752056
1.348337
-S19-

Cartesian coordinates (in Å, 1 Å = 100 pm) of the DFT-optimized geometry of (aS)-2a.
N
C
C
C
C
C
C
C
C
C
C
H
H
C
C
C
C
C
C
H
H
H
C
C
C
C
C
C
H
H
O
C
O
C
H
C
H
O
O
O
O
O
O
C
H
H
H
C
H
H
H
C
H
H
C
H
C
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
H
0.679684
-0.703051
1.160861
-1.111354
0.052599
-2.536078
-5.348083
-3.128485
-3.385697
-4.774231
-4.508387
-2.482095
-5.411739
0.088181
0.106882
0.076582
0.110299
0.118672
0.087499
0.055372
0.120251
0.080970
2.592342
5.408440
3.432051
3.186873
4.564444
4.831985
2.550103
5.489439
-2.922110
-1.575573
-1.270929
2.842866
3.483592
1.499592
0.977015
-6.708275
-5.149182
6.767813
5.207591
0.145841
0.166412
-4.353196
-3.722428
-5.055012
-3.713068
4.418432
5.127037
3.781194
3.787928
-0.001472
0.767820
-1.007382
-7.402823
-6.808401
7.462230
6.856374
7.660392
6.698825
8.270019
8.166936
8.769873
8.570237
9.362174
9.361322
-7.574177
-8.081247
-8.172386
-6.603526
-8.724523
-9.318360
-8.544728
-9.305098
-2.651007
-2.617131
-1.342151
-1.281341
-0.470523
-1.010976
-0.718634
0.266524
-2.128821
-1.980229
0.423606
1.129760
-2.855314
1.015141
3.788017
1.669243
1.776373
3.151623
3.073064
1.071292
1.292521
3.572536
-1.148797
-0.864159
-2.295014
0.130876
0.281925
-2.116361
0.999695
-2.979194
-3.423068
-3.752538
-4.929233
-3.602560
-4.476366
-3.765668
-4.710466
-0.611335
1.627238
-0.749882
1.478603
5.150328
4.093960
2.792307
2.738842
3.622608
2.957669
2.652972
3.477062
2.608648
2.815378
5.357397
6.052204
5.748098
0.039013
0.899136
-0.099329
0.746452
-1.091710
-1.475464
-1.940496
-0.608509
0.416089
1.123924
0.920283
-0.413601
-0.942667
-0.457356
-1.805563
-1.306552
0.524825
1.027983
1.226309
-0.319683
0.143935
0.145686
0.223833
0.226905
0.276470
0.242291
0.254111
0.328970
0.172629
0.173120
0.345086
0.397827
0.121119
0.349819
0.514319
1.590322
-0.844834
-0.726000
1.695868
2.496008
-1.815233
2.658792
0.239133
0.252672
0.167921
0.330330
0.347106
0.171480
0.402837
0.121459
0.091838
0.072405
-0.003288
0.086784
0.034111
0.076603
0.019366
0.336275
0.457300
0.337661
0.463466
0.336247
-1.726542
0.602936
1.499706
0.701386
-0.274061
0.595624
0.694316
1.487604
-0.287976
-1.074106
-1.421924
-1.283642
-0.763184
-1.088145
-0.762235
-1.103372
-1.905485
-2.262837
-1.575581
-2.749160
-0.178747
0.631111
-0.950245
0.224471
-1.919946
-2.762188
-1.606124
-2.273264
-0.185754
-0.956803
0.634291
0.202155
-S20-

Cartesian coordinates (in Å, 1 Å = 100 pm) of the DFT-optimized geometry of 2a-TS2.
N
C
C
C
C
C
C
C
C
C
C
H
H
C
C
C
C
C
C
H
H
H
C
C
C
C
C
C
H
H
O
C
O
C
H
C
H
O
O
O
O
O
O
C
H
H
H
C
H
H
H
C
H
H
C
H
C
H
C
H
H
H
C
H
H
H
C
H
H
H
C
H
H
H
0.757892
-0.619762
1.243320
-1.027214
0.149375
-2.454435
-5.258940
-3.056103
-3.300455
-4.677904
-4.424107
-2.451707
-5.294648
0.226869
0.385001
1.454996
-0.954866
-0.839912
1.558209
2.377471
-1.935636
2.526392
2.634916
5.373042
3.481480
3.168569
4.498688
4.845711
2.536280
5.504502
-2.825008
-1.479384
-1.157555
2.910726
3.547304
1.571143
1.045660
-6.619512
-4.948479
6.694951
4.958760
0.191078
-1.858933
-5.494926
-5.898013
-4.715040
-6.296884
5.256141
5.631888
4.348068
6.015941
-1.218247
-1.594137
-1.408014
-7.164811
-6.595747
7.544767
7.028891
8.815800
8.592105
9.308405
9.513430
7.806454
6.871075
8.431287
8.325062
-7.051269
-7.449465
-7.617641
-6.007857
-8.605776
-9.094060
-8.646224
-9.168907
-2.205242
-2.149267
-0.979297
-0.879846
-0.065292
-0.742091
-0.745486
0.207751
-1.755141
-1.741527
0.230525
0.940714
-2.526812
1.415901
4.195828
2.090735
2.192615
3.548977
3.475000
1.531820
1.747956
3.949372
-0.962914
-1.028927
-2.036747
-0.014856
-0.039481
-2.019868
0.744334
-2.812999
-2.844722
-3.169831
-4.233574
-3.155574
-3.971971
-3.251384
-4.095304
-0.718901
1.190908
-1.080628
0.921936
5.544995
4.468328
2.323002
2.983266
2.853188
2.021148
0.439960
1.299449
0.058593
-0.347727
5.698797
6.502448
5.919079
-0.954803
-0.349302
0.012502
0.955742
-0.077414
0.025897
-1.043439
0.717109
-0.117659
-0.098116
0.712384
-1.057802
-2.433910
-2.610887
-3.047538
-2.765357
-0.467743
-0.606806
0.594704
-1.028391
0.984708
1.024095
0.518432
0.598184
0.435038
0.323494
-0.170723
-0.526741
0.826506
0.609377
-0.759605
-1.046667
1.031342
0.555873
1.003167
0.721329
0.709057
0.907967
0.932916
0.736583
0.725190
1.051516
0.114855
-0.640818
0.525315
-0.787605
-1.166533
0.168986
-1.231384
0.510193
1.517796
1.554649
2.051396
1.221789
1.545141
1.384592
1.809565
-0.311029
-1.600658
-0.996902
-2.037374
1.184219
1.038629
-0.914190
-1.685641
-0.351867
-0.230593
-3.354406
-3.913856
-3.838591
-3.327637
1.393384
0.753834
2.453672
-1.642760
-2.355285
-0.538605
-0.748853
-1.371202
-2.437476
-1.214310
-1.085443
0.959670
1.528211
1.308641
1.179330
-2.001938
-3.007748
-1.292122
-1.989581
-1.584698
-2.555339
-1.325206
-0.830315
-S21-

References
1. Spartan ’10 for Windows, version 1.1.0 (Wavefunction Inc., Irvine, CA).
2. A. D. Becke, J. Chem. Phys., 1993, 98, 5648.
3. A. P. Scott and L. Radom, J. Phys. Chem., 1996, 100, 16502.
-S22-