Supporting Information. Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2008

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1 Supporting Information Copyright Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2008

2 Pyridine Catalyzed Stereoselective Addition of Acyclic 1,2-Diones to Acetylenic Ester: Synthetic and Theoretical Studies of An Unprecedented Rearrangement Abhilash N. Pillai, [a] Cherumuttathu H. Suresh*, [b] and Vijay Nair* [a,c] [a] Abhilash N. Pillai, Vijay Nair Organic Chemistry Section National Institute for Interdisciplinary Science and Technology (CSIR),)) Trivandrum Fax: (+) [b] Cherumuttathu H. Suresh, Computational Modeling and Simulation Section National Institute for Interdisciplinary Science and Technology (CSIR) Trivandrum Fax: (+) [c] Vijay Nair Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR) Bangalore

3 Supporting Information Contents General aspects General procedure for the preparation of benzil analogs General procedure for the reaction of benzil analogs with DMAD S2 S2 S3 1 H NMR Spectrums S4 Full reference for Gaussian 03 software S7

4 S2 Rotation experiment on 18 at B3LYP 6-31G(d) level PCM/B3LYP 6-31G(d) level structures of TS1 B3LYP 6-31+G(d,p) level structures of TS1 and TS2 B3LYP 6-31G(d) level structures S8 S8 S9 S9 General aspects: All reactions were carried out in oven-dried glassware under argon atmosphere. Progress of reaction was monitored by Thin Layer Chromatography (on glass plates coated with silica gel containing calciumsulfate as the binder; visualization was effected by exposure to UV light or iodine), while purification was effected by silica gel column chromatography (using mesh silica gel and mixtures of hexane- ethyl acetate as the eluent). NMR data were collected at room temperature in CDCl3 at an operating frequency of 300 (1H) and 75 (13C) MHz, respectively. Chemical shifts (δ) are reported relative to TMS (1H) or CDCl3 (13C). Melting points are uncorrected. Elemental analyses were done using a CHNS analyzer. High Resolution Mass Spectra were recorded under EI/HRMS (at 5000 resolution). Commercial grade solvents were distilled prior to use. Dimethyl acetylenedicarboxylate was used directly. General procedure for the preparation of benzil analogs: A solution of 0.50 g of thiamine hydrochloride in 2 ml water and 5 ml of 95% ethanol were taken in a reaction vial. To it 3M sodium hydroxide solution was added dropwise till a yellow color persists in the solution. Then aldehyde was added to it and the reaction mixture is heated at 60 C for 12 h. Adequate precautions should be taken to maintain the temperature below 65 C. After completion of the reaction, the mixture was poured into ice cold water and extracted with dichloromethane (3 x 10 ml). The combined organic extract was washed with water, brine and then dried over anhydrous sodium sulphate. After removal of the solvent on a rotary evaporator, 3 ml of concentrated nitric acid was

5 S3 added to it and refluxed for 5 h. After completion of the reaction, the mixture was poured into ice cold water and stirred well. The product which was precipitated in the solution was filtered, washed with sodium bicarbonate solution and water. Then it was dried and recrystallized from dichloromethanehexane solvent mixture. General procedure for the reaction of benzil analogs with DMAD: Benzil (1 equiv) and dimethyl acetylenedicarboxylate (1.2 equiv.) were taken in anhydrous dimethoxy ethane (5 ml), the solution was stirred under argon atmosphere and cooled to 10 C. Pyridine (20 mol%) was added and the mixture was gradually allowed to attain room temperature. The reaction was monitored by TLC and the solvent was distilled off in vacuo by using a rotary evaporator. The residue when subjected to column chromatography on a silica ( mesh) column first gave the unreacted benzil on using 5% ethyl acetate-hexane mixture as eluent. Subsequently, elution with 20% ethyl acetate-hexane mixture afforded the product which was recrystallized from dichloromethane-hexane solvent mixtures.

6 S4 Dimethyl (2Z)-2,3-dibenzoylbut-2-enedioate 7 Solvent: CDCl 3 /CCl 4 (7:3) 300MHz

7 S5 Dimethyl (2Z)-2,3-diacetylbut-2-enedioate 9 Solvent: CDCl 3 /CCl 4 (7:3) 300MHz

8 S6 Di-tert-butyl (2Z)-2,3-dibenzoylbut-2-enedioate 11 Solvent: CDCl 3 /CCl 4 (7:3) 300MHz

9 S7 Full reference for Gaussian 03 software (ref. 13) Gaussian 03, Revision C.02, Frisch, M. J. et al. ; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. J. A.; Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Yengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian, Inc.: Wallingford CT, 2004.

10 S8 Rotation Experiment done on Structure 18 at B3LYP/6-31G(d) level N MeOOC 34 o C COMe COMe COOMe Fully optimized geometry of 18 Rel.Energy = 0.0 kcal/mol N MeOOC 90 o COMe C COMe COOMe Rel. Energy = 11.2 kcal/mol COOMe N COMe C MeOCCOOMe Rel. Energy = 2.2 kcal/mol 180 o N C COOMe COMe 164 o N MeOC C COMe COOMe MeOC COOMe COOMe 90 o Fully optimized geometry Rel. Energy = 0.7 kcal/mol Rel. Energy = 11.8 kcal/mol B3LYP 6-31G(d) level optimized structure of 15 in THF using the PCM method.

11 S9 B3LYP 6-31+G(d,p) level structures of TS1 and TS2 TS1 (Activation barrier is 0.7 kcal/mol lower than the values reported in the text). TS2 (Activation barrier is 1.0 Kcal/mol higher than the values reported in the text). B3LYP 6-31G(d) level optimized structures. The Cartesian coordinates in Angstrom unit are written against each atom (atomic number is given in the fist column followed by X, Y, Z coordinates). At the end, the thermodynamic parameters are given in atomic unit. Compound

12 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= TS

13 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Compound

14 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= TS

15 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Compound

16 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= TS

17 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Compound

18 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= TS

19 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Compound

20 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= TS

21 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies= Compound

22 S Zero-point correction= (Hartree/Particle) Thermal correction to Energy= Thermal correction to Enthalpy= Thermal correction to Gibbs Free Energy= Sum of electronic and zero-point Energies= Sum of electronic and thermal Energies= Sum of electronic and thermal Enthalpies= Sum of electronic and thermal Free Energies=