Supporting Information

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1 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 216 Supporting Information γ-sultam-cored N,N-ligands in ruthenium(ii)-catalyzed asymmetric transfer hydrogenation of aryl ketones Slavko Rast, a Barbara Modec, b Michel Stephan a,c and Barbara Mohar* a a National Institute of Chemistry, Hajdrihova 19, 11 Ljubljana, Slovenia b Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113, 1 Ljubljana, Slovenia c Present address: PhosPhoenix SARL, 115, rue de l Abbé Groult, 7515 Paris, France barbara.mohar@ki.si Contents 1. Determination of X-ray structures... S1 2. GC & HPLC chromatograms... S H NMR and 13 C NMR spectra... S H, 13 C-HMBC analysis of trans-4... S H, 13 C-HMBC analysis of syn-6... S28 1. Determination of X-ray structures Data for crystals of [syn-(3s,1'r)-6] (S)-CSA, [anti-(3r,1'r)-6] (S)-CSA, and racemic trans-5 were collected using monochromated Mo-Kα radiation (λ =.7173 Å) and for crystals of S7-reduced (S7 ATH major reduction product) using Cu-Kα radiation (λ = Å). The coordinates of some or all of the non-hydrogen atoms were found via direct methods using the structure solution SHELXS-97 program. 1 Positions of the remaining nonhydrogen atoms were located by using a combination of least-squares refinement and difference Fourier maps in the SHELXL-97 program. 1 Except hydrogen atoms, all atoms were refined anisotropically. The absolute configuration of [syn-(3s,1'r)-6] (S)-CSA and [anti-(3r,1'r)-6] (S)-CSA were determined by refinement of the completed model together with the Flack x parameter 2 which refined to value of.(8) and.6(5), respectively, and as such confirmed that the refined coordinates represent in both cases the true enantiomorph. For S7-reduced, the value of the Flack x parameter refined to.1(3). In this case, the absolute configuration of one chiral center, i.e. C(1), was known prior to the analysis. Figures depicting the structures were prepared by Ortep3 3 and Mercury 4. The supplementary crystallographic data (atomic coordinates, anisotropic displacement parameters, and extended lists of interatomic distances and angles) are contained in cif files. 1 G. M. Sheldrick, SHELX-97. Programs for Crystal Structure Analysis; University of Göttingen: Göttingen, Germany, H. D. Flack, Acta Crystallogr., 1983, A39, L. Farrugia, J. Appl. Crystallogr., 1997, 3, C.F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor, M. Towler and J. van de Streek, J. Appl. Cryst., 26, 39, 453. SI1

2 Fig. S1 ORTEP drawing of racemic trans-5 at the 5% probability level (only one enantiomorph is shown). C 14 H 11 NO 2 S, F W 257.3, triclinic, space group P 1 (No. 2), a = (2), b = (2), c = 9.754(2) Å, α = (15), β = (17), γ = (15), V = 67.64(2) Å 3, Z = 2, T = 293(2) K, d calcd = 1.46 g cm 3, μ =.258 mm 1, 474 measured reflections, 2729 unique reflections (R int =.141), 171 refined parameters, R 1 [I > 2σ(I)] =.347, wr2 [all data] =.958. NH 3 O 3 S (3S) (1'R) NH S O 2 (1S) O (A) (B) Fig. S2 ORTEP drawing of [syn-(3s,1'r)-6] (S)-CSA at the 5% probability level; (A) cationic part, (B) anionic part. Fig. S3 Hydrogen-bonding pattern in [syn-(3s,1'r)-6] (S)-CSA: each NH 3 + group is engaged in H-bonds with three SO 3 moieties with N O contacts in the 2.979(3) 2.997(4) Å range. 5 Infinite chains which run parallel to b-axis are thus formed. Color code: green - cations, blue - anions. 5 The sum of the van der Waals radii for O atoms is 3.7 Å. Data were taken from B. Douglas, D. McDaniel and J. Alexander, Concepts and Models of Inorganic Chemistry, 3 rd Ed.; John Wiley and Sons: New York, 1994; p. 12. SI2

3 NH 3 O 3 S (3R) (1'R) NH S O 2 (1S) O (A) (B) Fig. S4 ORTEP drawing of [anti-(3r,1'r)-6] (S)-CSA at the 5% probability level; (A) cationic part, (B) anionic part. Structural similarities exist between [anti-(3r,1'r)-6] (S)-CSA and [syn-(3s,1'r)-6] (S)-CSA. Both crystallize in monoclinic space group P 2 1 with alike packing arrangement. Hydrogen bonds between NH 3 + and SO 3 groups in [anti-(3r,1'r)-6] (S)-CSA also link cations and anions into infinite chains which run parallel to b-axis. The respective N O contacts in [anti-(3r,1'r)-6] (S)-CSA, i.e., 2.835(2) 2.861(2) Å, are slightly shorter than those observed for [syn-(3s,1'r)-6] (S)-CSA. OH S7-reduced CO 2 Me Fig. S5 ORTEP drawing of S7 ATH major reduction product at the 5% probability level. C 11 H 12 O 3, Fw , orthorhombic, space group P (No. 19), a = 4.792(1), b = (2), c = (3) Å, V = (3) Å 3, Z = 4, T = 293(2) K, d calcd = g cm 3, μ =.745 mm 1, measured reflections, 27 unique reflections (R int =.331), 141 refined parameters, R 1 [I > 2σ(I)] =.418, wr2 [all data] =.126. Fig. S6 In S7-reduced, the hydroxyl groups are engaged in H-bonds. Each molecule forms two H-bonds with two adjacent molecules. The respective O O contacts are 2.672(12) Å. 5 Infinite chains are formed thereby. The chains propagate along a-axis. SI3

4 2. GC & HPLC chromatograms (R)-1-Phenylethanol. Ee was determined by chiral GC analysis 6 on Chiralsil-DEX CB column (25m.25mm), 12 OH C (isothermal), t R : 4.6 min (R), 4.8 min (S). 77.8% ee: 11, uv SR128_SR86E2_AcPh_4h_4C1.DATA 1, 9, 8, 7, 6, 5, 4, 3, 2, 1, (R)-1-Phenylethanol 1 (S)-1-Phenylethanol -1, -2, RT [min] 5.25 Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 (R)-1-Phenylethanol (S)-1-Phenylethanol Total Racemate: 26, uv AK411_rac_mix_Acetophenone_DexCB_99142.DATA 24, 22, 2, 18, 16, 14, 12, 1, 8, 6, 4, 2, (R)-Enantiomer (S)-Enantiomer RT [min] Peak Name Time [Min] Height [uv] Area [uv.min] Area % 1 (R)-Enantiomer (S)-Enantiomer Total For chiral GC analysis, see: A. Kišić, M. Stephan and B. Mohar, Adv. Synth. Catal., 215, 357, SI4

5 Ethyl (R)-3-hydroxy-3-phenylpropionate. Ee was determined by chiral GC analysis 7 on Chiralsil-DEX CB OH (25m.25mm), 14 C (isothermal); racemate, t R : 14.6 min (S), 14.9 min (R). CO 2 Et 92.2% ee: 8 75 uv SR138_EtBenzoylacetate_cymene_35C_2h1.DATA 7 65 E E1 15 RT [min] 16 Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 (S) (R) Total % ee (S): 7, 6,5 6, 5,5 5, uv MJ39_3_DexCB_iso142.DATA 4,5 4, 3,5 3, (S)-Enantiomer 2,5 2, 1,5 1, (R)-Enantiomer RT [min] Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 (S)-Enantiomer (R)-Enantiomer Total For chiral GC analysis, see: D. Šterk, M.S. Stephan and B. Mohar, Tetrahedron: Asymmetry, 22, 13, SI5

6 (R)-1-Indanol. Ee was determined by chiral HPLC analysis on Chiralcel OD column (25 cm). Eluent hexane/2- OH PrOH = 98:2, flow rate 1. ml/min, λ = 254 nm, t R : 22.6 min (S), 26.2 min (R) % ee: 9 UV detektor AK923_OD+pred_98_2_254nm Retention Time , mau 4 4 mau ,317 2,5 21, 21,5 22, 22,5 23, 23,5 24, 24,5 25, 25,5 26, 26,5 27, 27,5 28, 28,5 29, Minutes Peak Retention [min] Area Area % Height Height % E1 22, ,61 514,81 E2 25, , ,19 Totals Racemate: 26 UV detektor AK266_rac_mix_OD+predkolona_98_2_254nm Retention Time , , mau mau Minutes Peak Retention [min] Area Area % Height Height % E1 22, , ,52 E2 26, , ,48 Totals SI6

7 (R)-1-Tetralol. Ee was determined by chiral GC analysis on Chiralsil-DEX CB column (25m.25mm), 13 C OH (isothermal), t R : 13.3 min (S), 13.8 min (R) % ee: 6, 5,5 5, 4,5 4, 3,5 3, 2,5 2, 1,5 1, 5 uv E2 AK929_R1_1-tetralone_isotherm13_DexCB1.DATA TI ON E RT [min] Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 E E Total Racemate: 11, 1, 9, uv AK214_rac_mix_Alpha-tetralone_isotherm13_DexCB_24141.DATA 8, E1 7, E2 6, 5, 4, 3, 2, 1, -1, RT [min] Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 E E Total SI7

8 (R)-4-Chromanol. Ee was determined by chiral HPLC analysis on Chiralcel OD-H column (25 cm). Eluent OH hexane/2-proh = 95/5, flow rate 1. ml/min, λ = 22 nm, t R : 1. min (S), 11.7 min (R). 6 O 99.4% ee: 1 UV detektor AK926_OD_H+pred_95_5_22nm Retention Time , mau 5 5 mau ,933 9, 9,2 9,4 9,6 9,8 1, 1,2 1,4 1,6 1,8 11, 11,2 11,4 11,6 11,8 12, 12,2 12,4 12,6 12,8 13, 13,2 13,4 13,6 13,8 14, Minutes Peak Retention [min] Area Area % Height Height % E1 9, ,26 226,31 E2 11, , ,69 Totals Racemate: 1 UV detektor AK798_rac_mix_OD_H(25cm)+pred_95_5_22nm Retention Time 1 9 9, , mau 5 5 mau ,4 8,6 8,8 9, 9,2 9,4 9,6 9,8 1, 1,2 1,4 1,6 1,8 11, 11,2 11,4 11,6 11,8 12, 12,2 12,4 12,6 12,8 13, 13,2 13,4 13,6 13,8 14, Minutes Peak Retention [min] Area Area % Height Height % E1 9, , ,79 E2 11, , ,21 Totals SI8

9 (1R,2R)-2-Methoxycarbonyl-1-indanol. Ee was determined by chiral GC analysis on Chiralsil-DEX CB column OH (25m.25mm), 13 C (isothermal); racemates (cis/trans = 55:45), t R : 33.7 min [cis (R,R)], 34.8 min [cis (S,S)], 45. min (trans-1), 5. min (trans-2). 6 CO 2 Me 99.5% ee, cis:trans 97:3 3,6 uv SR713A1_DexCB_13C_ DATA 3,4 D1 3,2 3, 2,8 2,6 2,4 2,2 2, 1,8 1,6 1,4 1,2 1, TI ON D2 D3 D4 TI OFF RT [min] Racemates: 3,2 uv 3, 2,8 2,6 2,4 2,2 2, 1,8 1,6 1,4 1,2 1, Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 (R,R) (S,S) trans trans Total D1 D2 D3 D4 AK267_rac_mix_indanone_methyl_ester_isotherm13_DexCB1.DATA RT [min] Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 (R,R) (S,S) trans trans Total SI9

10 (1R,3S)-3-Methoxycarbonyl-1-indanol. Ee was determined by chiral GC analysis on Chiralsil-DEX CB column OH (25m.25mm), 13 C (isothermal); racemates (cis/trans = 97:3), t R : 16.8 min [cis (1S,3R)], 18.6 min [cis (1R,3S)], 24.1 min (trans-1), 25.2 min (trans-2). CO 2 Me 98.8% ee (cis), >99% ee (trans): 2, 1,9 1,8 1,7 1,6 1,5 1,4 1,3 uv D2 SR78b_EtOAc_3h_DexCB_14C_ DATA 1,2 1,1 1, TI ON D1 D3 TI OFF RT [min] Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 (S,R) (R,S) trans Total Racemates: 5, uv SR75rac_DexCB_14C_ DATA 4,5 4, D1 3,5 D2 3, 2,5 2, 1,5 1, 5 TI ON D3 D4 TI OFF -5 RT [min] Peak Name Time [Min] Height [uv] Area [uv.min] Area [%] 1 (S,R) (R,S) trans trans Total SI1

11 (1R,2R)-2-Methoxycarbonyl-1-tetralol. Dr (cis/trans = 97.6:2.4) was determined by 1 H NMR; ee (cis 99.4%) was OH determined by chiral HPLC analysis on Chiralpak IB-3 column (25 cm). Eluent hexane/2- CO 2 Me PrOH = 97/3, flow rate 1. ml/min, λ = 22 nm; racemates: t R : 15.4 min (trans-1), 17.4 min [cis (R,R)], 19.7 min (trans-2), 32.7 min [cis (S,S)]. cis/trans = 98:2, >99% ee (cis) 55 5 UV detektor MJ4-3_ChiralpakIB-3_97,3_22nm Retention Time 17, mau mau ,7 33, Minutes Retention Time Area Area % Height Height % 17, , ,35 19, , ,39 33, ,3 124,26 Totals , , Mixture prepared by weighing both corresponding ATH products derived from enantiomeric catalysts: UV detektor MJ44+Mj4-3_ChiralpakIB-3_97,3_22nm Retention Time 17, mau , mau ,767 19, Minutes Retention Time Area Area % Height Height % 15, , ,64 17, , ,51 19, , ,32 32, , ,53 Totals , 53 1, SI11

12 (1R,3RS)-3-Methoxycarbonyl-1-tetralol. Dr (cis/trans = 5:5) was determined by 1 H NMR; ee (99% for cis) was OH determined by 19 F NMR (CDCl 3 ) of the (R)-Mosher ester (prepared from (S)-Mosher s acid CO 2 Me cis/trans = 5:5, 99% ee (cis) chloride): δ [cis (1R,3R)], 72. [cis (1S,3S)], (trans; stereoisomers not separated). 19 F NMR (CDCl 3 ) of the (R)-Mosher ester Racemates: SI12

13 (1R,4RS)-4-Methoxycarbonyl-1-tetralol. Dr (cis/trans = 5:5) was determined by 1 H NMR; ee was determined OH by chiral GC analysis on Chiralsil-DEX CB column (25m.25mm), 15 C (isothermal); racemates (cis/trans = 72:28), t R : 21.1 min (cis 1R,4S), 21.9 min (trans 1R,4R), 22.7 min (cis 1S,4R), 24.4 min (trans 1S,4S). CO 2 Me >99% ee (cis), >99% ee (trans): 2,6 uv SR713A3_DexCB_15C_ DATA 2,4 D3 2,2 2, 1,8 D2 1,6 1,4 1,2 1, RT [min] Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 D D Total Racemates (cis/trans 72:28): 2,6 2,4 uv D1 MJ4_DexCB_15C_ DATA 2,2 D2 2, 1,8 1,6 1,4 1,2 1, D3 D4 RT [min] Peak Name Time [Min] Height [uv] Area [uv.min] Area % [%] 1 D D D D Total SI13

14 3. 1 H NMR and 13 C NMR spectra SI14

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27 4. 1 H, 13 C-HMBC analysis of trans-4 HO Ph 5-exo-type cyclization O Ph 6-endo-type cyclization H OH Ph NH S O 2 SO 2 NH 2 trans-3 NH S O 2 trans-4 Fig. S7 6-endo-tet- vs. 5-exo-tet-type cyclization of trans-3; 1 H, 13 C-HMBC analysis revealing chemical shift correlation between the marked proximal aromatic hydrogen of the 1,1-dioxo-benzo-1,2-thiazinane core and the carbon atom bearing the hydroxyl group. SI27

28 5. 1 H, 13 C-HMBC analysis of syn-6 NH 2 NH S O 2 rac syn-6 Fig. S8 1 H, 13 C-HMBC analysis of syn-6 revealing chemical shift correlation between the marked proximal aromatic hydrogen of the 1,1-dioxo-benzo-1,2-thiazolidine core and the carbon atom bearing the α-aminobenzyl group. SI28