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1 Electronic Supporting Information Asymmetric Epoxidation of Alkylidenemalononitriles: Key-Step for One-Pot Approach to Enantioenriched 3-Substituted Piperazin-2-ones Sara Meninno, Andreu Vidal-Albalat and Alessandra Lattanzi* Dipartimento di Chimica e Biologia, Università di Salerno, Via Giovanni Paolo II, 84084, Fisciano, Italy, lattanzi@unisa.it Table of contents General Methods... S2 Experimental Procedures and Compounds Characterization... S3 Synthesis of catalysts... S3 General procedure for the synthesis of catalysts 7a-e, 4... S3 General procedure for the synthesis of racemic epoxides 2a-k... S7 General procedure for the asymmetric synthesis of epoxides 2a-k... S7 Table S1... S8 Table S2... S9 Table S3... S10 Table S4... S11 General procedure for one-pot asymmetric epoxidation/ring-opening reaction to piperazin-2-ones S16 NMR Spectra... S21 HPLC Chromatograms... S61 S1

2 General Methods All reactions requiring dry or inert conditions were conducted in flame-dried glassware under a positive pressure of nitrogen. THF and DCM were freshly distilled prior to use respectively over metallic Na and calcium hydride and stored under nitrogen, all other solvents were dried over molecular sieves. Molecular sieves (Aldrich Molecular Sieves, 3 Å, 1.6 mm pellets) were activated under vacuum at 200 C overnight. Reactions were monitored by thin layer chromatography (TLC) on Macherey-Nagel pre-coated silica gel plates (0.25 mm) and visualized by UV light and, when necessary, by phosphomolybdic acid, ninhydrin, KMnO 4 staining solutions or I 2 vapor. Flash chromatography was performed on Merck silica gel (60, particle size: mm). 1 H NMR and 13 C NMR spectra were recorded on Bruker Avance-400 spectrometer, Bruker Avance-300 or Bruker Avance-250 spectrometer in CDCl 3 or methanol-d 4 as solvent at room temperature. Chemical shifts for protons are reported using residual solvent protons ( 1 H NMR: δ = 7.26 ppm for CDCl 3, δ = 3.33 ppm for methanol-d 4 ) as internal standard. Carbon spectra were referenced to the shift of the 13 C signal of CDCl 3 (δ =77.0 ppm), CD 3 OD (δ = 49.0 ppm). The following abbreviations are used to indicate the multiplicity in NMR spectra: (s) singlet; (d) doublet; (t) triplet; (q) quartet; (dd) double doublet; (ddd) doublet of doublet of doublet; (dt) doublet of triplets; (td) triplet of doublets; (m) multiplet; (bs) broad signal. Optical rotation of compounds was performed on a Jasco P-2000 digital polarimeter using WI (Tungsten-Halogen) lamp (λ = 589 nm). FTIR spectra were recorded as thin films on KBr plates using Bruker Tensor 27 spectrometer and absorption maxima are reported in wavenumber (cm -1 ). ESI-MS was performed using a Bio-Q triple quadrupole mass spectrometer (Micromass, Manchester, UK) equipped with an electrospray ion source. Elemental analyses were carried out by using Flash EA 1112 (Thermo Electron Corporation) analyzer. Melting points were measured with a Stuart Model SMP 30 melting point apparatus and are uncorrected. Petrol ether (PE) refers to light petroleum ether (boiling point C). Anhydrous toluene, acetonitrile and all starting materials (unless otherwise noted) were purchased from Aldrich and used as received. Alkenes 1a-i 1 and alkenes 1j-k 2 were prepared by using general procedures reported in the literature. Catalysts 1s and HQN were purchased from Aldrich and compound 5 from Strem Chemicals and used as received. Enantiomeric ratio of epoxides 2 and compounds 8 was determined by HPLC (Waters-Breeze 2487, UV dual λ absorbance detector and 1525 Binary HPLC Pump) using Daicel chiral columns. 1 Pande, A.; Ganesan, K.; Jain,A. K.; Gupta, P. K.; Malhotra, R. C. Org. Process Res. Dev. 2005, 9, Yamashita, K.; Tanaka, T.; Hayashi, M. Tetrahedron 2005, 61, S2

3 Experimental Procedures and Compounds Characterization Synthesis of catalysts Cinchona alkaloids were purchased from Aldrich and used as received. Amine-thioureas eqnt, ecdt, ehqnt, eqdt were synthesized according to the literature. 3 Catalysts eqns 4, eqnu 5, 3, 6 6, 7 2s, 8 3s, 9 4s 6b-c,10,11 and the compounds A1 12 and A 13 2 are known compounds, they were prepared according to the literature. General procedure for the synthesis of catalysts 7a-e, 4 To a stirred solution of A 1 or A 2 (401 mg, 1.1 mmol) under nitrogen atmosphere in dry THF (2 ml) a solution of appropriate chiral 2-amino-1,2-diphenylethanol or methylbenzylamine (1 mmol) in dry THF (2 ml) was added via syringe. The mixture was stirred at 40 C for h, monitored by TLC (eluent diethyl ether/meoh 8/2). The products 7a-e were isolated by flash chromatography (eluent: diethyl ether to diethyl ether /MeOH 90/10). Catalyst 7c is a known compound and spectral data were consistent with those in the literature. 14 Thiourea 7a derived from quinine and (1S, 2S)-2-Amino-1,2-diphenylethanol 3 Vakulya, B.; Varga S.; Csámpai, A.; Soós T. Org. Lett. 2005, 7, Yang, W.; Du, D.-M. Org. Lett. 2010, 12, (a) Miyaji, R.; Asano K.; Matsubara, S. Org. Lett. 2013, 15, (b) Amere, M.; Lasne, M.-C.; Rouden, J. Org. Lett. 2007, 9, (c) Wu, W.; Min, L.; Zhu, L.; Lee, C.-S. Adv. Synth. Catal. 2013, 353, (a) Marcelli, T.; van der Haas, R. N. S.; van Maarseveen, J. H.; Hiemstra, H. Angew. Chem. Int. Ed. 2006, 45, 929. (b) Li, H.; Wang, Y.; Tang, L.; Deng, L. J. Am. Chem. Soc. 2004, 126, (c) Liu, X.; Li, H.; Deng, L. Org. Lett. 2005, 7, Meninno, S.; Croce, G.; Lattanzi, A. Org. Lett., 2013, 15, Honjo, T.; Sano, S.; Shiro, M.; Nagao, Y. Angew. Chem. Int. Ed. 2005, 44, Li, W.; Wu, W.; Yu, F.; Huang, H.; Liang, X.; Ye, J. Org. Biomol. Chem. 2011, 9, Montagnac, A.; Litaudon, M; Pais, M. Phytochemistry 1997, 46, Heidelberger, M.; Jacobs, W. A. J. Am. Chem. Soc. 1919, 41, Li, N.-K.; Liu, Z.-M.; Huang, X.-F.; Zhang, J.-X.; Chen, X.; Wang, Y.; Wang, X.-W. RSC Adv. 2013, 3, Bassas, O.; Huuskonen, J.; Rissanen, K.; Koskinen, A. M. P. Eur. J. Org. Chem. 2009, Ma, H.; Matsuzaki, K.; Yang, Y.-D.; Tokunaga, E.; Nakane, D.; Ozawa, T.; Masuda, H.; Shibata, N. Chem. Commu. 2013, 49, S3

4 White solid, 463 mg, 80% yield. mp C. [α] 27 D = (c 0.56, CHCl 3 ). FTIR ν max (KBr)/cm , 2948, 2866, 1623, 1510, 1474, 1454, 1263, 1242, 1228, 1029, 775, H NMR (CDCl 3, 400 MHz): δ 8.54 (bs, 1H), 7.96 (d, 1H, J = 9.4 Hz), 7.69 (s, 1H), 7.36 (d, 1H, J = 8.8 Hz), (partially overlapped by CDCl 3, m, 12H), (m, 1H) partially overlapped with 5.70 (br, 1H) and 5.39 (br, 1H), (m, 3H), 3.94 (s, 3H), 3,18 (br, 1H), 2.91 (br, 1H), (m, 2H), (m, 1H), 1.87 (br, 1H), (m, 3H), (m, 2H), (m, 1H). 13 C NMR (CD 3 OD, 100 MHz): δ 184.2, 159.6, 148.1, 145.0, 143.2, 142.1, 131.0, 130.1, 129.0, 128.6, 128.2, 127.5, 123.9, 120.8, 115.2, 104.3, 77.4, 65.0, 61.2, 56.6, 56.4, 42.8, 40.4, 28.7, 28.1, MS (ESI m/z) [MH +, 100%]. Thiourea 7b derived from quinine and (1R, 2R)-2-Amino-1,2-diphenylethanol 1-((1S,2S)-2-hydroxy-1,2-diphenylethyl)-3-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5- vinylquinuclidin-2-yl)methyl)thiourea (7a) 1-((1R,2R)-2-hydroxy-1,2-diphenylethyl)-3-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5- vinylquinuclidin-2-yl)methyl)thiourea (7b) Yellow solid, 54.1 mg, 68% yield (the reaction was carried out at mmol scale of A 1 ). mp C. [α] 27 D = (c 0.51, CHCl 3 ). FTIR ν max (KBr)/cm , 2931, 2864, 1624, 1541, 1508, 1474, 1454, 1262, 1242, 1229, 1029, 757, H NMR (CDCl 3, 400 MHz): δ 8.70 S4

5 Thiourea 7d derived from quinine and (1S, 2R)-2-Amino-1,2-diphenylethanol (d, 1H, J = 4.4 Hz), 8.01 (d, 1H, J = 9.1 Hz), 7.61 (s, 1H), 7.52 (br, 1H), 7.38 (dd, 1H, J = 9.3, 2.0 Hz), (m, 1H), (m, 7H), (m, 4H), (m, 1H) partially overlapped with 5.38 (bs, 2H), (m, 2H), 4.81 (d, 1H, J = 5.8 Hz), 3.90 (s, 3H), (m, 3H), (m, 1H), (m, 1H), 1.87 (br, 1H), (m, 3H), (m, 2H), (m, 1H). 13 C NMR (CD 3 OD, 100 MHz): δ 184.0, 159.5, 148.1, 145.0, 142.9, 142.3, 141.3, 131.1, 130.0, 129.0, 128.9, 128.7, 128.4, 128.1, 128.0, 123.7, 121.2, 115.1, 104.1, 78.1, 65.7, 61.7, 56.6, 56.5, 42.7, 40.6, 28.7, 28.3, MS (ESI m/z) [MH +, 21%]. 1-((1R,2S)-2-hydroxy-1,2-diphenylethyl)-3-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5- vinylquinuclidin-2-yl)methyl)thiourea (7d) White solid, 80.8 mg, 85% yield (the reaction was carried out at mmol scale of A 1 ). mp C. [α] 27 D = (c 0.57, CHCl 3 ). FTIR ν max (KBr)/cm , 2944, 2865, 1623, 1538, 1511, 1475, 1453, 1262, 1242, 1229, 1029, 755, H NMR (CDCl 3, 400 MHz): δ 8.76 (d, 1H, J = 4.5 Hz), 8.05 (d, 1H, J = 9.2 Hz), 7.61 (bs, 1H), (m, 3H), (m, 5H), 7.06 (s, 2H), (m, 2H), (m, 2H), 5.61 (ddd, 1H, J = 17.2, 10.0, 7.4 Hz), 5.30 (bs, 2H), 5.06 (bs, 1H), (m, 2H), 3.94 (s, 3H), 3.01 (br, 1H), 2.81 (br, 1H), (m, 1H), (m, 1H), (m, 5H), (m, 1H), (m, 1H), (m, 1H). 13 C NMR (CD 3 OD, 100 MHz): δ 183.3, 159.6, 148.2, 145.1, 142.5, 142.4, 138.9, 131.0, 130.1, 129.6, 129.1, 129.0, 128.7, 128.5, 128.1, 127.5, 123.8, 121.0, 115.1, 104.2, 79.5, 76.2, 65.0, 61.8, 56.8, 56.6, 42.9, 40.6, 28.8, 28.4, MS (ESI m/z) [MH +, 100%]. S5

6 Thiourea 7e derived from quinidine and (1R, 2R)-2-Amino-1,2-diphenylethanol 1-((1R,2R)-2-hydroxy-1,2-diphenylethyl)-3-((R)-(6-methoxyquinolin-4-yl)((1S,2R,4S,5R)-5 vinylquinuclidin-2-yl)methyl)thiourea (7e) White solid, 53.5 mg, 67% yield (the reaction was carried out at mmol scale of A 2 ). mp C. [α] 27 D = (c 0.55, CHCl 3 ). FTIR ν max (KBr)/cm , 2940, 2872, 1623, 1534, 1509, 1474, 1455, 1433, 1242, 1227, 1029, 754, H NMR (CDCl 3, 300 MHz): δ 8.56 (bs, 1H), 7.96 (d, 1H, J = 9.2 Hz), 7.61 (bs, 1H), (partially overlapped by CDCl 3, m, 11H), 6.79 (br, 2H), 5.84 (ddd, 1H, J = 17.3, 10.4, 6.0 Hz), 5.42 (br, 2H) partially overlapped with (m, 2H), 4.81 (d, 1H, J = 5.9 Hz), 3.96 (s, 3H), (m, 4H), (m, 1H), (m, 4H), (m, 2H), (m, 1H). 13 C NMR (CD 3 OD, 75 MHz): δ 189.1, 159.6, 148.1, 145.0, 143.8, 143.2, 141.2, 131.0, 130.1, 129.0, 128.7, 128.2, 127.5, 124.1, 120.0, 115.5, 104.1, 77.4, 65.2, 65.0, 61.4, 56.6, 40.9, 39.8, 28.6, 26.8, MS (ESI m/z) [MH +, 100%]. Thiourea 4 derived from quinine and (S)-( )-α-methylbenzylamine 1-((S)-(6-methoxyquinolin-4-yl)((1S,2S,4S,5R)-5-vinylquinuclidin-2-yl)methyl)-3-((S)-1- phenylethyl)thiourea (4) Pale yellow solid, 62.0 mg, 79% yield (the reaction was carried out at 0.16 mmol scale of A 1 ). mp C. [α] 26 D = (c 0.55, CHCl 3 ). FTIR ν max (KBr)/cm , 1622, 1534, 1508, 1474, 1453, 1432, 1347, 1262, 1242, 1228, 1083, 1030, 918, 853, 759, H NMR (CDCl 3, 400 MHz): δ 8.74 (d, 1H, J = 4.5 Hz), 8.03 (d, 1H, J = 9.2 Hz), 7.58 (s, 1H), (m, 7H), 6.76 (bs, 1H), (m, 1H), 5.29 (bs, 1H), (m, 3H), 3.94 (s, 3H), S6

7 2.62 (m, 3H), (m, 1H), (m, 1H), (m, 1H), (m, 2H), 1.39 (d, 3H, J = 6.4 Hz), (m, 2H), (m, 1H). 13 C NMR (CDCl 3, 100 MHz): δ 181.9, 157.8, 147.7, 144.8, 142.5, 140.7, 131.9, 128.9, 128.5, 127.7, 126.8, 126.0, 125.7, 121.7, 114.8, 101.9, 55.7, 55.1, 54.4, 51.3, 40.2, 39.2, 30.3, 29.7, 27.5, 27.2, 25.7, MS (ESI m/z) [MH +, 100%]. General procedure for the synthesis of racemic epoxides 2a-k In a sample vial containing a solution of alkylidenemalononitrile 1 (1 mmol) in anhydrous toluene (10 ml) (or anhydrous acetonitrile (10 ml) for the compound 1f), 2-piperidinemethanol (23 mg, 0.2 mmol) followed by TBHP (~5.5 M in decane, 240 µl, 1.3 mmol) were added. The reaction was stirred at 0 C for hours, monitored by TLC (eluent PE/ ethyl acetate 90/10 or 95/5 for compounds 2j-k). The products were isolated (32-91% yields) by flash chromatography (eluting from PE/ ethyl acetate 100/1 to 90/10). General procedure for the asymmetric synthesis of epoxides 2a-k A sample vial was charged with alkylidenemalononitrile 1 (0.15 mmol) and catalyst 7a (8.7 mg, mmol) in anhydrous toluene (3 ml). Then cumene hydroperoxide (tech. 80%, 33 μl, 0.18 mmol) was added and the solution was stirred at -20 C until completion, monitored by TLC (eluent PE/ ethyl acetate 90/10 or 95/5 for compounds 2j-k). Purification of the crude mixture by flash chromatography (eluting with PE/ ethyl acetate 100/1 for 2a,g,j-k or from PE/ ethyl acetate 100/1 to 98/2 for 2c-d,h-i to 95/5 for 2b,e-f) gave enantioenriched epoxides 2a-k (47-90% yields). Absolute configuration of epoxides was assumed to be (S) in analogy to that indirectly determined on compound 2a on the basis of characterization data of previously reported compounds 8a,d 18 and 8g. 20 S7

8 Table S1. Screening of catalysts in the asymmetric epoxidation of alkene 1a a entry cat time (h) yield (%) b er (%) c 1 d 1s :55 2 2s :52 3 3s : HQN : s :60 a Reactions were carried out at 0.1 mmol scale of 1a (C 0.2 M) using TBHP (1.2 equiv). b Determined by 1 H NMR analysis with 1,3,5-(MeO) 3 C 6 H 3 as an internal standard. c Determined by chiral HPLC analysis. d Reaction carried out with 20 mol % of 1s. S8

9 Table S2. Solvent screening a entry solvent time (h) yield (%) b er (%) c 1 ClC 6 H :28 2 CHCl :32 3 m-xylene :23 4 benzene :23 5 hexane : THF :39 7 1,3,5-(CH 3 ) 3 C 6 H : CCl :25 9 hexafluorobenzene :29 10 α,α,α-trifluorotoluene :32 11 ethyl acetate :35 12 CH 3 CN :46 a Reactions were carried out at 0.1 mmol scale of 1a (C 0.2 M) using TBHP (1.2 equiv). b Determined by 1 H NMR analysis with 1,3,5-(MeO) 3 C 6 H 3 as an internal standard. c Determined by chiral HPLC analysis. S9

10 Table S3. Screening of oxidants and reaction conditions in the asymmetric epoxidation of alkene 1a a entry R T ( C) C 1a (M) time (h) yield (%) b er (%) c 1 cumyl rt : CH 3 (Ph) 2 C- 15 rt :28 3 (CH 3 CH 2 ) 2 PhC- 16 rt : Ph 3 C- 17 rt :34 5 d H rt : cumyl -20 C :15 7 t-bu -20 C :27 8 cumyl -40 C :27 9 cumyl -20 C : e cumyl -20 C :18 11 f cumyl -20 C :18 12 g cumyl -30 C :18 a Reactions were carried out at 0.1 mmol scale of 1a (C 0.2 M) using 1.2 equiv. of oxidant. b Determined by 1 H NMR analysis with 1,3,5-(MeO) 3 C 6 H 3 as an internal standard. c Determined by chiral HPLC analysis. d Reaction carried out with 1.3 equiv. of H 2 O 2 (50 wt. % in H 2 O). e Reaction carried out with 5 mol% of 7a. f Reaction carried out with 32 mg of 3Å MS. g Reaction carried out with 38 mg of 3Å MS. 15 (a) Grossi, L.; Strazzari, S. J. Org. Chem. 2000, 65, (b) Richardson, W. H.; Hodge, V. F. J. Org. Chem. 1970, 35, Feng, X.; Yuan, Y.-Q.; Cui, H.-L.; Jiang, K.; Chen Y.-C. Org. Biomol. Chem. 2009,7, Bissing, D. E.; Matuszac, C. A.; McEwen, W. E. J. Am. Chem. Soc. 1964, 86, S10

11 Table S4. Screening of additives in the asymmetric epoxidation of alkene 1a a entry Additive (mol%) time (h) yield (%) b er (%) c : Benzoic acid (10 mol%) : Nitrophenol (10 mol%) : Methoxyphenol (10 mol%) :38 5 PhCH 2 OH (10 mol%) : d (1R)-(-)-10-Camphorsulfonic :32.5 acid monohydrate (5 mol%) 7 Pd(CH 3 CO 2 ) 2 (5 mol%) :35 8 Sodium acetate (20 mol%) :25 a Reactions were carried out at 0.1 mmol scale of 1a (C 0.2 M) using 1.2 equiv. of CHP. b Determined by 1 H NMR with an internal standard. c Determined by chiral HPLC analysis. d Reaction carried out at C 0.15M of 1a with 26 mg of 3Å MS. (S)-3-phenyloxirane-2,2-dicarbonitrile (2a) White solid, 19.9 mg, 78% yield. mp C. [α] 24 D = (c 0.56, CH 3 CN), er 85.2:14.8. FTIR ν max (KBr)/cm , 3039, 2257, 1498, 1457, 1399, 1382, 1318, 1298, 1268, 1192, 893, 875, 762, 697, 637, H NMR (CDCl 3, 400 MHz): δ (m, 5H), 4.71 (s, 1H). 13 C NMR (CDCl 3, 100 MHz): δ 131.4, 129.1, 127.5, 126.8, 111.6, 110.2, 65.8, Elemental analysis calcd (%) for C 10 H 6 N 2 O: C, 70.58; H, 3.55; N, 16.46; found C, 70.84; H, 3.64; N, HPLC analysis with Chiralcel OD-H column, 90:10 n-hexane:2-propanol, 1 ml/min, 254 nm; minor enantiomer t R = 9.8 min, major enantiomer t R = 10.9 min. S11

12 (S)-3-(4-(trifluoromethyl)phenyl)oxirane-2,2-dicarbonitrile (2b) White solid, 26.4 mg, 74% yield. mp C. [α] 28 D = (c 0.22, EtOH), er 86:14. FTIR ν max (KBr)/cm , 2854, 2258, 1427, 1326, 1171, 1131, 1113, 1069, 1018, 892, 850, 829, 762, H NMR (CDCl 3, 400 MHz): δ 7.77 (d, 1H, J = 8.1 Hz), 7.58 (d, 1H, J = 8.1 Hz), 4.78 (s, 1H). 13 C NMR (CDCl 3, 75 MHz): δ (q, 2 J C-F = 33 Hz), 131.3, 128.8, (q, 3 J C- F = 3.6 Hz), (q, 1 J C-F = 271 Hz), 111.1, 109.7, 64.7, Elemental analysis calcd (%) for C 11 H 5 F 3 N 2 O: C, 55.47; H, 2.12; N, 11.76; found C, 55.73; H, 2.19; N, HPLC analysis with Chiralcel OD-H column, 90:10 n-hexane:2-propanol, 1 ml/min, 254 nm; minor enantiomer t R = 12.8 min, major enantiomer t R = 15.9 min. (S)-3-(3-bromophenyl)oxirane-2,2-dicarbonitrile (2c) White solid, 33.8 mg, 90% yield. mp C. [α] 27 D = (c 0.70, CHCl 3 ), er 83:17. FTIR ν max (KBr)/cm , 2850, 2258, 1597, 1573, 1476, 1436, 1378, 1262, 1191, 1073, 997, 907, 877, 852, 786, 693, 671, H NMR (CDCl 3, 400 MHz): δ (m, 1H), 7.60 (s, 1H), (m, 2H), 4.68 (s, 1H). 13 C NMR (CDCl 3, 100 MHz): δ 134.6, 130.7, 129.9, 129.7, 125.2, 123.2, 111.2, 109.7, 64.7, Elemental analysis calcd (%) for C 10 H 5 BrN 2 O: C, 48.22; H, 2.02; N, 11.25; found C, 48.47; H, 1.98; N, HPLC analysis with Chiralcel OD- H column, 90:10 n-hexane:2-propanol, 1 ml/min, 220 nm; minor enantiomer t R = 13.3 min, major enantiomer t R = 14.5 min. S12

13 (S)-3-(naphthalen-2-yl)oxirane-2,2-dicarbonitrile (2d) White solid, 23.1 mg, 70% yield. mp C. [α] 27 D = (c 0.53, CHCl 3 ), er 81.6:18.4. FTIR ν max (KBr)/cm , 2849, 2262, 1635, 1511, 1401, 1385, 1339, 1271, 1193, 870, 856, 814, 741, 667, 609, H NMR (CDCl 3, 400 MHz): δ (m, 4H), (m, 2H), 7.47 (d, 1H, J = 8.5 Hz), 4.88 (s, 1H). 13 C NMR (CDCl 3, 100 MHz): δ 134.5, 132.6, 129.3, 128.3, 128.0, 127.9, 127.5, 127.3, 124.7, 122.4, 115.6, 110.2, 66.1, Elemental analysis calcd (%) for C 14 H 8 N 2 O: C, 76.35; H, 3.66; N, 12.72; found C, 76.29; H, 3.75; N, HPLC analysis with Chiralcel OD-H column, 90:10 n-hexane:2-propanol, 1 ml/min, 254 nm; minor enantiomer t R = 19.5 min, major enantiomer t R = 17.1 min. (S)-3-(4-nitrophenyl)oxirane-2,2-dicarbonitrile (2e) Pale yellow solid, 20.8 mg, 64% yield. mp C. [α] 27 D = (c 0.31, CHCl 3 ), er 85.5:14.5. FTIR ν max (KBr)/cm , 2857, 2261, 1607, 1520, 1345, 1190, 1104, 892, 877, 857, 814, 751, 695, H NMR (CDCl 3, 250 MHz): δ 8.38 (d, 2H, J = 8.6 Hz), 7.66 (d, 2H, J = 8.6 Hz), 4.84 (s, 1H). 13 C NMR (CDCl 3, 100 MHz): δ 149.8, 134.0, 128.0, 124.4, 110.8, 109.4, 64.3, Elemental analysis calcd (%) for C 10 H 5 N 3 O 3 : C, 55.82; H, 2.34; N, 19.53; found C, 56.10; H, 2.41; N, HPLC analysis with Chiralcel OD-H column, 80:20 n- hexane:2-propanol, 1 ml/min, 254 nm; minor enantiomer t R = 19.8 min, major enantiomer t R = 25.9 min. S13

14 (S)-3-(4-cyanophenyl)oxirane-2,2-dicarbonitrile (2f) White solid, 23.3 mg, 80% yield. mp C. [α] 27 D = (c 0.52, CH 3 CN), er 90.4:9.6. FTIR ν max (KBr)/cm , 2850, 2231, 1637, 1421, 1380, 1291, 1193, 876, 847, 832, H NMR (CDCl 3, 250 MHz): δ 7.81 (d, 2H, J = 8.3 Hz), 7.58 (d, 2H, J = 8.3 Hz), 4.77 (s, 1H). 13 C NMR (CDCl 3, 62.5 MHz): δ 132.9, 132.3, 127.6, 117.5, 115.4, 110.8, 109.5, 64.5, Elemental analysis calcd (%) for C 11 H 5 N 3 O: C, 67.69; H, 2.58; N, 21.53; found C, 68.02; H, 2.50; N, HPLC analysis with Chiralcel OD-H column, 80:20 n-hexane:2-propanol, 1 ml/min, 220 nm; minor enantiomer t R = 17.0 min, major enantiomer t R = 26.1 min. (R)-3-(4-cyanophenyl)oxirane-2,2-dicarbonitrile (2f) [α] 27 D = (c 0.62, CH 3 CN), er 9.9:90.1. HPLC analysis with Chiralcel OD-H column, 80:20 n-hexane:2-propanol, 1 ml/min, 220 nm; minor enantiomer t R = 28.3 min, major enantiomer t R = 17.9 min. (S)-3-(4-chlorophenyl)oxirane-2,2-dicarbonitrile (2g) White solid, 24.5 mg, 80% yield. mp C. [α] 25 D = (c 0.68, CHCl 3 ), er 87.7:12.3. FTIR ν max (KBr)/cm , 2850, 2260, 1599, 1495, 1427, 1307, 1289, 1275, 1190, 1091, 1013, 893, 868, 830, 823, 716, 625, H NMR (CDCl 3, 250 MHz): δ 7.48 (d, 2H, J = 8.5 Hz), 7.38 (d, 2H, J = 8.5 Hz), 4.70 (s, 1H). 13 C NMR (CDCl 3, 62.5 MHz): δ 137.7, 129.5, 128.1, 125.9, 111.3, 109.9, 65.1, Elemental analysis calcd (%) for C 10 H 5 ClN 2 O: C, 58.70; H, 2.46; N, 13.69; found C, 58.98; H, 2.55; N, HPLC analysis with Chiralcel OD-H column, 90:10 n-hexane:2-propanol, 1 ml/min, 254 nm; minor enantiomer t R = 12.6 min, major enantiomer t R = 15.3 min. S14

15 (S)-3-(o-tolyl)oxirane-2,2-dicarbonitrile (2h) White solid, 18.0 mg, 65% yield. mp C. [α] 27 D = (c 0.57, CHCl 3 ), er 82.8:17.2. FTIR ν max (KBr)/cm , 2869, 2256, 1492, 1460, 1381, 1290, 1276, 1195, 891, 878, 766, 722, 634, H NMR (CDCl 3, 250 MHz): δ (m, 4H), 4.77 (s, 1H), 2.46 (s, 3H). 13 C NMR (CDCl 3, 100 MHz): δ 136.9, 130.8, 130.7, 126.5, 126.3, 125.2, 115.6, 110.0, 64.4, 41.0, Elemental analysis calcd (%) for C 11 H 8 N 2 O: C, 71.73; H, 4.38; N, 15.21; found C, 72.06; H, 4.50; N, HPLC analysis with Chiralcel OD-H column, 90:10 n-hexane:2-propanol, 1 ml/min, 254 nm; minor enantiomer t R = 10.8 min, major enantiomer t R = 12.2 min. (S)-3-(3-methoxyphenyl)oxirane-2,2-dicarbonitrile (2i) White solid, 27.0 mg, 90% yield. mp C. [α] 27 D = (c 0.69, CH 3 CN), er 86.6:13.4. FTIR ν max (KBr)/cm , 2841, 2258, 1604, 1588, 1493, 1459, 1437, 1388, 1326, 1261, 1192, 1153, 1040, 873, 787, 768, H NMR (CDCl 3, 400 MHz): δ 7.40 (t, 1H, J = 8.0 Hz), (m, 2H), 6.91 (s, 1H), 4.68 (s, 1H), 3.84 (s, 3H). 13 C NMR (CDCl 3, 100 MHz): δ 160.0, 130.3, 128.8, 119.0, 117.2, 111.7, 111.5, 110.1, 65.6, 55.4, Elemental analysis calcd (%) for C 11 H 8 N 2 O 2 : C, 66.00; H, 4.03; N, 13.99; found C, 66.29; H, 3.92; N, HPLC analysis with Chiralpak IC column, 90:10 n-hexane:2-propanol, 1 ml/min, 254 nm; minor enantiomer t R = 6.8 min, major enantiomer t R = 8.2 min. S15

16 3-cyclohexyloxirane-2,2-dicarbonitrile (2j) Pale yellow wax, 22.2 mg, 84% yield. [α] 27 D = -9.2 (c 0.82, CHCl 3 ), er 82:18. FTIR ν max (KBr)/cm , 2857, 2255, 1654, 1453, 1420, 1278, 1198, 971, 898, 887, 831, H NMR (CDCl 3, 250 MHz): δ 3.39 (d, 1H, J = 8.5 Hz), (m, 5H), (m, 6H). 13 C NMR (CDCl 3, 62.5 MHz): δ 111.8, 110.8, 69.4, 38.7, 38.4, 29.4, 27.8, 25.5, Elemental analysis calcd (%) for C 10 H 12 N 2 O: C, 68.16; H, 6.86; N, 15.90; found C, 67.94; H, 6.98; N, HPLC analysis with Chiralcel OD-H column, 98:2 n-hexane:2-propanol, 1 ml/min, 210 nm; minor enantiomer t R = 6.2 min, major enantiomer t R = 5.6 min. 3-heptyloxirane-2,2-dicarbonitrile (2k) Colorless oil, 13.5 mg, 47% yield. [α] 25 D = (c 0.80, CHCl 3 ), er 74.9:25.1. FTIR ν max (KBr)/cm , 2858, 2256, 1726, 1687, 1467, 1410, 1379, 1201, H NMR (CDCl 3, 300 MHz): δ 3.64 (t, 1H, J = 6.0 Hz), (m, 2H), (m, 3H), (m, 5H), (m, 5H). 13 C NMR (CDCl 3, 100 MHz): δ 111.8, 110.7, 66.0, 38.8, 31.5, 29.3, 28.91, 28.87, 25.2, 22.5, Elemental analysis calcd (%) for C 11 H 16 N 2 O: C, 68.72; H, 8.39; N, 14.57; found C, 68.99; H, 8.53; N, HPLC analysis with Chiralcel OD-H column, 98:2 n-hexane:2- propanol, 1 ml/min, 210 nm; minor enantiomer t R = 7.0 min, major enantiomer t R = 6.1 min. General procedure for one-pot asymmetric epoxidation/ring-opening reaction to piperazin- 2-ones In a sample vial containing alkylidenemalononitrile 1 (0.15 mmol) and catalyst 7a (8.7 mg, mmol) in anhydrous toluene (3 ml), cumene hydroperoxide (tech., 80%, 33 μl, 0.18 mmol) was added. The reaction was stirred at -20 C for hours monitored by TLC till the formation of epoxide 2 was complete. After completion, toluene was removed and anhydrous acetonitrile (5 ml) was added. Then 2.5 equivalents of 1,2-diamines (0.375 mmol) (or 2.0 equivalents of (1R,2R)-1,2-diaminocyclohexane for compounds 8f,g) were added to the reaction mixture. The reaction mixture was stirred at room temperature for hours, monitored by TLC (eluent PE/ ethyl acetate 9/1 to check if the epoxide has been consumed). After completion, the mixture was diluted with 20 ml of ethyl acetate and washed twice with saturated NH 4 Cl S16

17 solution and then with water. The organic layer was dried over anhydrous Na 2 SO 4 and concentrated under reduced pressure. The reaction mixture was purified by flash chromatography (eluent: PE/ ethyl acetate 98/2 to 9/1, then CHCl 3 for compounds 8a-c,e) to give products 8a,c-e in 60-76% yield. For piperazin-2-ones 8d, 8f,g, acetonitrile was removed under reduced pressure and the crude mixture was purified directly by flash chromatography (85-98% yield) (for compound 8d: eluent ethyl acetate then ethyl acetate/ methanol 98:2 to 90:10; for compounds 8f,g: eluent CH 2 Cl 2 then CH 2 Cl 2 / MeOH 50/0.2 to 98/2 to elute compound 8g and to 95/5 to elute compound 8f). (R)-1,4-dibenzyl-3-phenylpiperazin-2-one (8a) Ph N O N Ph Ph Data for this compound were consistent with those reported in the literature. 18 Yellow wax, 32.1 mg, 60% yield. [α] 25 D = (c 0.17, CHCl 3 ), er 85.9:14.1. FTIR ν max (KBr)/cm , 2852, 1653, 1495, 1453, 756, H NMR (CDCl 3, 400 MHz): δ 7.58 (d, 2H, J = 7.2 Hz), (m, 13H), 4.65 and 4.56 (ABq, 2H, J = 14.5 Hz), 4.16 (s, 1H), 3.77 (d, 1H, J = 13.4 Hz), 3.48 (td, 1H, J = 11.2, 4.0 Hz), 3.16 (d, 1H, J = 13.4 Hz) partially overlapped with 3.12 (dt, 1H, J = 12.0, 3.0 Hz), 2.97 (dt, 1H, J = 12.0, 3.2 Hz), 2.49 (td, 1H, J = 11.1, 3.5 Hz). 13 C NMR (CDCl 3, 100 MHz): δ 168.9, 139.9, 138.3, 137.4, 129.5, 129.2, 129.1, 128.9, 128.7, 128.6, 128.4, 127.9, 127.6, 71.7, 59.4, 50.7, 47.1, HPLC analysis with Chiralcel OD column, 90:10 n-hexane:2- propanol, 0.5 ml/min, 254 nm; minor enantiomer t R = 30.0 min, major enantiomer t R = 25.1 min (a) Baek, J.; Jang J. I.; Park, Y. S. Bull. Korean Chem. Soc. 2011, 32, (b) Jang, J. I.; Kang, S. Y.; Kang, K. H.; Park, Y. S. Tetrahedron 2011, 67, S17

18 (R)-4-(1,4-dibenzyl-3-oxopiperazin-2-yl)benzonitrile (8b) Ph N O N Ph CN Pale yellow solid, 38.3 mg, 67% yield. mp C. [α] 26 D = (c 0.18, CHCl 3 ), er 88.9:11.1. FTIR ν max (KBr)/cm , 2852, 2228, 1646, 1495, 1454, 753, H NMR (CDCl 3, 300 MHz): δ (m, 4H), (m, 10H), 4.62 and 4.50 (ABq, 2H, J = 14.5 Hz), 4.19 (s, 1H), 3.68 (d, 1H, J = 13.4 Hz), 3.48 (td, J = 11.7, 4.0 Hz), 3.18 (d, 1H, J = 13.4 Hz) partially overlapped with 3.13 (dt, 1H, J = 11.9, 3.0 Hz), 2.99 (dt, 1H, J = 11.9, 3.0 Hz), 2.51 (td, 1H, J = 11.7, 3.3 Hz). 13 C NMR (CDCl 3, 62.5 MHz): δ 167.0, 145.1, 136.9, 136.3, 132.3, 129.8, , , 128.5, 128.2, 127.7, 127.5, 118.8, 111.8, 70.7, 59.1, 50.3, 46.7, Elemental analysis calcd (%) for C 25 H 23 N 3 O: C, 78.71; H, 6.08; N, 11.02; found C, 79.00; H, 6.17; N, HPLC analysis with Chiralcel OD-H column, 80:20 n-hexane:2-propanol, 1 ml/min, 254 nm; minor enantiomer t R = 24.9 min, major enantiomer t R = 15.9 min. (R)-1,4-dibenzyl-3-(4-chlorophenyl)piperazin-2-one (8c) Pale yellow wax, 41.0 mg, 70% yield. [α] 25 D = (c 0.18, CHCl 3 ), er 87.8:12.2. FTIR ν max (KBr)/cm , 2854, 1647, 1491, 1454, 1217, 1091, 757, H NMR (CDCl 3, 300 MHz): δ 7.52 (d, 2H, J = 8.4 Hz), 7.36 (d, 2H, J = 8.4 Hz), (m, 10H), 4.62 and 4.52 (ABq, 2H, J = 14.6 Hz), 4.11 (s, 1H), 3.73 (d, 1H, J = 13.4 Hz), 3.46 (td, J = 11.2, 4.0 Hz), 3.14 (d, 1H, J = 13.4 Hz) partially overlapped with 3.11 (dt, 1H, J = 11.5, 3.1 Hz), 2.96 (dt, 1H, J = 11.8, 3.2 Hz), 2.48 (td, 1H, J = 11.6, 3.5 Hz). 13 C NMR (CDCl 3, 75 MHz): δ 167.9, 138.0, 137.4, 136.6, 133.7, 130.3, , , 128.4, 128.2, 127.6, 127.4, 70.5, 58.9, 50.3, 46.7, Elemental analysis calcd (%) for C 24 H 23 ClN 2 O: C, 73.74; H, 5.93; N, 7.17; found C, 74.05; H, 6.06; N, S18

19 7.02. HPLC analysis with Chiralcel OD-H column, 90:10 n-hexane:2-propanol, 1 ml/min, 220 nm; minor enantiomer t R = 15.7 min, major enantiomer t R = 12.6 min. (R)-3-phenylpiperazin-2-one (8d) Data for this compound were consistent with those reported in the literature. 18 Pale yellow solid, 22.6 mg, 85% yield. mp (Decomp.). [α] 27 D = -9.1 (c 0.66, CHCl 3 ), er 85.9:14.1. FTIR ν max (KBr)/cm , 2851, 1649, 1491, 1453, 1334, 757, H NMR (CDCl 3, 400 MHz): δ (m, 5H), 7.11 (bs, 1H), 4.56 (s, 1H), (m, 1H), (m, 1H), 3.13 (dt, 1H, J = 12.6, 4.4 Hz), 3.04 (ddd, 1H, J = 12.5, 8.4, 4.1 Hz), 2.61 (bs, 1H). 13 C NMR (CDCl 3, 100 MHz): δ 171.0, 139.4, 128.5, 128.3, 127.9, 63.9, 43.2, HPLC analysis with Chiralcel OD-H column, 90:10 n-hexane:2-propanol, 1 ml/min, 220 nm; minor enantiomer t R = 37.9 min, major enantiomer t R = 42.0 min. (R)-1-benzyl-3-phenylpiperazin-2-one (8e) Ph N O N H Data for this compound were consistent with those reported in the literature. 18,19 Yellow wax, 30.4 mg, 76% yield. [α] 27 D = -7.2 (c 0.54, CHCl 3 ), er 85.1:14.9. FTIR ν max (KBr)/cm , 2854, 1641, 1495, 1453, 753, H NMR (CDCl 3, 400 MHz): δ (m, 10H), 4.66 (m, 3H), 3.45 (ddd, 1H, J = 11.6, 8.5, 4.5 Hz), 3.25 (dt, 1H, J = 11.8, 4.3 Hz), 3.16 (dt, 1H, J = 12.4, 4.6 Hz), 3.06 (ddd, 1H, J = 12.6, 8.5, 4.3 Hz). 13 C NMR (CDCl 3, 75 MHz): δ 168.7, 139.7, 137.2, 129.5, 129.3, 129.1, 129.0, 128.9, 128.7, 128.6, 128.4, 128.0, 127.9, 64.3, 50.8, 47.6, HPLC analysis with Chiralcel OD column, 80:20 n-hexane:2-propanol, 1 ml/min, 220 nm; minor enantiomer t R = 14.6 min, major enantiomer t R = 25.4 min. 18 Ph 19 (a) Rao, D. V. N. S.; Dandala, R.; Handa, V. K.; Sivakumaran, M.; Naidu, A. Arkivoc 2006, xiv, 1. (b) Guo, B. S.; Yang, Y. S.; Ji, R. Y. Chin. Chem. Lett. 2003, 14, 365. S19

20 (3R,4aR,8aR)-3-phenyloctahydroquinoxalin-2(1H)-one (8f) Yellow solid, 29.0 mg, 84% yield. mp C. [α] 26 D = (c 0.53, CHCl 3 ), er > 99.5:0.5. FTIR ν max (KBr)/cm , 2851, 1648, 1465, 1377, 757, H NMR (CDCl 3, 400 MHz): δ 7.41 (d, 2H, J = 7.3 Hz), 7.36 (t, 2H, J = 7.3 Hz), 7.29 (t, 1H, J = 7.0 Hz), 6.41 (s, 1H), 4.73 (s, 1H), (m, 1H), 2.59 (td, 1H, J = 10.0, 3.2 Hz), 2.28 (bs, 1H), (m, 4H), (m, 4H). 13 C NMR (CDCl 3, 100 MHz): δ 170.8, 140.4, 128.6, 127.7, 127.5, 62.0, 59.0, 52.6, 31.5, 30.7, 24.6, MS (ESI m/z) [MH +, 100%]. HPLC analysis with Chiralcel OD-H column, 80:20 n-hexane:2-propanol, 1 ml/min, 220 nm; major enantiomer t R = 12.6 min. (3S,4aR,8aR)-3-phenyloctahydroquinoxalin-2(1H)-one (8g) Data for this compound were consistent with those reported in the literature. 20 Pale yellow solid, 4.8 mg, 14% yield. mp C. [α] 24 D = (c 0.29, CHCl 3 ), er > 99.5:0.5. FTIR ν max (KBr)/cm , 2858, 1654,1451, 1340, 753, H NMR (CDCl 3, 400 MHz): δ 7.43 (d, 2H, J = 7.1 Hz), (m, 3H), 5.83 (s, 1H), 4.66 (s, 1H), (m, 1H), 2.71 (td, 1H, J = 10.7, 3.5 Hz), (m, 4H), 1.69 (bs, 1H), (m, 4H). 13 C NMR (CDCl 3, 100 MHz): δ 170.8, 139.6, , , 127.9, 65.2, 58.8, 58.4, 31.3, 30.5, 24.5, MS (ESI m/z) [MH +, 100%]. HPLC analysis with Chiralcel OD-H column, 80:20 n-hexane:2- propanol, 1 ml/min, 220 nm; major enantiomer t R = 15.8 min. 20 Aggarwal, V. K.; Barrell, J. K.; Worrall J. M.; Alexander, R. J. Org. Chem. 1998, 63, S20

21 NMR Spectra 1 H NMR in CDCl 3 (400 MHz) S21

22 13 C NMR in CD 3 OD (100 MHz) S22

23 1 H NMR in CDCl 3 (400 MHz) S23

24 13 C NMR in CD 3 OD (100 MHz) S24

25 1 H NMR in CDCl 3 (400 MHz) S25

26 13 C NMR in CD 3 OD (100 MHz) S26

27 1 H NMR in CDCl 3 (300 MHz) S27

28 13 C NMR in CD 3 OD (75 MHz) S28

29 1 H NMR in CDCl 3 (400 MHz) S29

30 13 C NMR in CDCl 3 (100 MHz) S30

31 1 H NMR in CDCl 3 (400 MHz) S31

32 13 C NMR in CDCl 3 (100 MHz) S32

33 1 H NMR in CDCl 3 (400 MHz) S33

34 13 C NMR in CDCl 3 (75 MHz) S34

35 1 H NMR in CDCl 3 (400 MHz) S35

36 13 C NMR in CDCl 3 (100 MHz) S36

37 1 H NMR in CDCl 3 (400 MHz) S37

38 13 C NMR in CDCl 3 (100 MHz) S38

39 1 H NMR in CDCl 3 (250 MHz) S39

40 13 C NMR in CDCl 3 (100 MHz) S40

41 1 H NMR in CDCl 3 (250 MHz) S41

42 13 C NMR in CDCl 3 (62.5 MHz) S42

43 1 H NMR in CDCl 3 (250 MHz) S43

44 13 C NMR in CDCl 3 (62.5 MHz) S44

45 1 H NMR in CDCl 3 (250 MHz) S45

46 13 C NMR in CDCl 3 (100 MHz) S46

47 1 H NMR in CDCl 3 (400 MHz) S47

48 13 C NMR in CDCl 3 (100 MHz) S48

49 1 H NMR in CDCl 3 (250 MHz) S49

50 13 C NMR in CDCl 3 (62.5 MHz) S50

51 1 H NMR in CDCl 3 (300 MHz) S51

52 13 C NMR in CDCl 3 (100 MHz) S52

53 1 H NMR in CDCl 3 (300 MHz) S53

54 13 C NMR in CDCl 3 (62.5 MHz) S54

55 1 H NMR in CDCl 3 (300 MHz) S55

56 13 C NMR in CDCl 3 (75 MHz) S56

57 1 H NMR in CDCl 3 (400 MHz) S57

58 13 C NMR in CDCl 3 (100 MHz) S58

59 1 H NMR in CDCl 3 (400 MHz) S59

60 13 C NMR in CDCl 3 (100 MHz) S60

61 HPLC Chromatograms S61

62 S62

63 S63

64 S64

65 S65

66 S66

67 S67

68 S68

69 S69

70 S70

71 S71

72 S72

73 S73

74 S74

75 S75

76 S76

77 S77

78 S78

79 S79

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