Alinmihiş, Ligiamirabelagolban, Cipriani.Raţ, Elena Bogdan, Anamariaterec* and Ion Grosu*

Supporting Information

Synthesis and Stereochemistry of New Spiro[5.5]undecane Derivatives with 1,3-Dioxane, 1,3-Dithiane or 1,3-Oxathiane Rings

AlinMihiş, LigiaMirabelaGolban, CiprianI.Raţ, Elena Bogdan, AnamariaTerec* and Ion Grosu*

Babes-BolyaiUniversity, Center of Supramolecular Organic and Organometallic Chemistry, Cluj-Napoca, 11 Arany Janos, 400028, Cluj-Napoca, Romania;

Contents

Theoretical calculations details21

References22

Figure S1. Optimized structure (ADF BP86/TZ2P) of 12.23

Figure S2. Optimized structure (ADF BP86/TZ2P) of the ax-ax isomer of 15.23

Figure S3. Optimized structure (ADF BP86/TZ2P) of the ax-eq isomer of 15.24

Figure S4. Optimized structure (ADF BP86/TZ2P) of the eq-eq isomer of 15.24

Table S1. Cartesian coordinates (Å) of the optimized structure (ADF BP86/TZ2P) of the 1,3-dioxane-1,3-dithiane derivative 12. 25

Table S2. Cartesian coordinates (Å) of the optimized structure (ADF BP86/TZ2P) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15. 26

Table S3. Cartesian coordinates (Å) of the optimized structure (ADF BP86/TZ2P) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15. 27

Table S4. Cartesian coordinates (Å) of the optimized structure (ADF BP86/TZ2P) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15. 28

Table S5. Cartesian coordinates (Å) of the optimized structure (GAMESS B3LYP/6-31G(d)) of the 1,3-dioxane-1,3-dithiane derivative 12. 29

Table S6. Cartesian coordinates (Å) of the optimized structure (GAMESS B3LYP/6-31G(d)) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15. 30

Table S7. Cartesian coordinates (Å) of the optimized structure (GAMESS B3LYP/6-31G(d)) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15. 31

Table S8. Cartesian coordinates (Å) of the optimized structure (GAMESS B3LYP/6-31G(d)) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15. 32

Table S9. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the 1,3-dioxane-1,3-dithiane derivative 12. 33

Table S10. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15. 34

Table S11. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15. 35

Table S12. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15. 36

Theoretical calculations details

Theoretical calculations for 12 and the ax-ax, ax-eq, and eq-eq isomers of 15 were carried out using the ADF2008.1e,S1–S3 GAMESS 2010 R2,S4,S5 and ORCA 2.7 software packages.

For the geometry optimizations calculations performed with with ADF software package the BP86 functional and a TZ2P basis set with a large frozen core were used. The energy minimum of the optimized structures was confirmed by frequency calculations performed at the same theory level as the geometry optimization calculations. The frequencies were calculated analytically and for all compounds the IR spectra showed a number of imaginary frequencies: 1 for 12 at –5.182 cm–1, 2 for ax-ax15 at –8.975 and –6.804 cm–1, 1 for ax-eq15 at –4.921 cm–1, and 1 for eq-eq10b at –13.881 cm–1. Calculations of the gradients along the corresponding normal modes of the imaginary frequencies revealed that they emerge from the summation of the numerical errors.

The calculations with the GAMESS software package were performed using the B3LYP functional (with VWN5 for the local correlation part) and using the 6-31G basis set augmented with one d function for all the atoms.

Geometry optimizations and frequency calculations with ORCA were carried out using B3LYP functional and the 6-31G(d,p) basis set as implemented in the software package. For all the calculations the Grid 4 and TightSCF options were selected. The frequency calculations on the 15 isomers revealed that the optimized geometries are energy minima. In the frequency calculation of 12 a negative value was obtained at –12.42 cm–1. The small value corresponding to the negative calculated frequency suggests that it is likely to emerge from the summation of the numerical errors.

The cartesian coordinates of the optimized structures are listed in Tables S1 - S12 and graphical representations of the structures optimized with ADF are shown in Figures S1 - S4.

References

(S1) G. te Velde, F. M. Bickelhaupt, S. J. A. van Gisbergen, C. Fonseca Guerra, E. J. Baerends, J. G. Snijders and T. Ziegler, J. Comp. Chem. 2001, 22, 931.

(S2) C. Fonseca Guerra, J. G. Snijders, G. te Velde, E. J. Baerends, Theor. Chem. Acc. 1998, 99, 391.

(S3) E. J. Baerends, J. Autschbach, A. Bérces, F. M. Bickelhaupt, C. Bo, P. M. Boerrigter, L. Cavallo, D. P. Chong, L. Deng, R. M. Dickson, D. E. Ellis, M. van Faassen, L. Fan, T. H. Fischer, C. Fonseca Guerra, S. J. A. van Gisbergen, A. W. Götz, J .A. Groeneveld, O. V. Gritsenko, M. Grüning, F. E. Harris, P. van den Hoek, C. R. Jacob, H. Jacobsen, L. Jensen, G. van Kessel, F. Kootstra, M. V. Krykunov, E. van Lenthe, D. A. McCormack, A. Michalak, J. Neugebauer, V. P. Nicu, V. P. Osinga, S. Patchkovskii, P. H. T. Philipsen, D. Post, C. C. Pye, W. Ravenek, J. I. Rodríguez, P. Ros, P. R. T. Schipper, G. Schreckenbach, J. G. Snijders, M. Solà, M. Swart, D. Swerhone, G. te Velde, P. Vernooijs, L. Versluis, L. Visscher, O. Visser, F. Wang, T.A. Wesolowski, E. M. van Wezenbeek, G. Wiesenekker, S. K. Wolff, T. K. Woo, A. L. Yakovlev, T. Ziegler, ADF2008.01e, SCM, Theoretical Chemistry, Vrije Universiteit, Amsterdam, The Netherlands,

(S4) M. W. Schmidt, K. K.Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis, J. A. Montgomery J. Comput. Chem.1993,14, 1347.

(S5) M. S. Gordon, M. W. Schmidt, Advances in electronic structure theory: GAMESS a decade later, , in "Theory and Applications of Computational Chemistry: the first forty years" C. E. Dykstra, G. Frenking, K. S. Kim, G. E. Scuseria (editors), Elsevier, Amsterdam, 2005, pp. 1167-1189.

(S6) Neese, F. ORCA, version 2.7; University of Bonn: Bonn, Germany, 2008.

Figure S1. Optimized structure (ADF BP86/TZ2P) of 12.

Figure S2. Optimized structure (ADF BP86/TZ2P) of the ax-ax isomer of 15.

Figure S3. Optimized structure (ADF BP86/TZ2P) of the ax-eq isomer of 15.

Figure S4. Optimized structure (ADF BP86/TZ2P) of the eq-eq isomer of 15.

Table S1. Cartesian coordinates (Å) of the optimized structure (ADFBP86/TZ2P) of the 1,3-dioxane-1,3-dithiane derivative 12.

Table S2. Cartesian coordinates (Å) of the optimized structure (ADFBP86/TZ2P) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15.

Table S3. Cartesian coordinates (Å) of the optimized structure (ADFBP86/TZ2P) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15.

Table S4. Cartesian coordinates (Å) of the optimized structure (ADFBP86/TZ2P) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15.

Table S5. Cartesian coordinates (Å) of the optimized structure (GAMESSB3LYP/6-31G(d)) of the 1,3-dioxane-1,3-dithiane derivative 12.

Table S6. Cartesian coordinates (Å) of the optimized structure (GAMESSB3LYP/6-31G(d)) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15.

Table S7. Cartesian coordinates (Å) of the optimized structure (GAMESSB3LYP/6-31G(d)) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15.

Table S8. Cartesian coordinates (Å) of the optimized structure (GAMESSB3LYP/6-31G(d)) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15.

Table S9. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the 1,3-dioxane-1,3-dithiane derivative 12.

Table S10. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the ax-ax isomer of the bis(1,3-oxathiane) derivatives 15.

Table S11. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the ax-eq isomer of the bis(1,3-oxathiane) derivatives 15.

Table S12. Cartesian coordinates (Å) of the optimized structure (ORCA B3LYP/6-31G(d,p)) of the eq-eq isomer of the bis(1,3-oxathiane) derivatives 15.