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1 Supporting Information Macrocyclic Diorganotin Complexes of -Amino Acid Dithiocarbamates as Hosts for Ion-Pair Recognition Jorge Cruz-Huerta, a Manuel Carillo-Morales, a Ericka Santacruz-Juárez, a Irán F. Hernández-Ahuactzi, a Jaime Escalante-García, a Carolina Godoy-Alcantar, a Jorge A. Guerrero-Alvarez, a Herbert Höpfl, a, * Hugo Morales-Rojas, a Mario Sánchez b a) Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, C.P Cuernavaca, México. hhopfl@ciq.uaem.mx. b) Facultad de Química, Universidad de Guanajuato, Noria Alta s/n, C.P Guanajuato, México. Preparation and spectroscopic data of ligands L2 and L3 Scheme S1. Synthesis of 3-(benzylamino)propionic acid L2. Scheme S2. Reaction sequence for the benzylation of 4-aminobutyric acid. Figure S1. Calculated (B3LYP/SBKJC(d,p)) and experimental (KBr) IR spectra for compound 5. Figure S2: Perspective view of the supramolecular synthon (a) in the crystal structure of compound 6 that gives rise to 1 1D molecular arrangement (b). Figure S3. Figure S2. Changes of the absortion spectra during the titration of 7 (6.7 x 10-5 M) with different quantities of AcOTBA (0-3.6 x10-2 M) in CHCl 3. The arrows indicate the spectral changes occurring in response to an increasing concentration of AcOTBA. Figure S4. Plots for the titration of compounds 6 and 7 with AcOTBA in CHCl 3. Figure S Sn NMR spectra before and after addition of AcOTBA for compounds a) 6 and b) 7. Figure S6. Complexation induced shifts (CIS) for the 1 H NMR signals of the N-CH 2 -spacer (left) and CH 2 -COO groups (right) in compound 6 upon addition of AcOTBA in Corresponding author. Fax: (+52) address: hhopfl@ciq.uaem.mx (H. Höpfl) S1

2 a solution in CDCl 3 at 25 o C. The solid curve is fitting to a 1:1 binding model from which K as was calculated. Table S1. Atomic coordinates and selected geometric parameters for the calculated molecular structure of compound 5 (B3LYP/SBKJC(d,p)). Table S2. Calculated and experimental vibrational frequencies for [Me 2 Sn(L3-dtc)] 3 (5). Table S3. Selected NMR spectroscopic data for compounds L1HCl, L2, L3 and 1-7 (in CDCl 3, ppm). Table S4. Atomic coordinates and selected geometric parameters for the calculated molecular structure of compound 1 (B3LYP/SBKJC(d,p)). S2

3 Preparation and spectroscopic data of ligands L2 and L3 3-(Benzylamino)propionic acid L2 Benzylamine (3.60 g, 33.6 mmol), methyl acrylate (3.18 g, 36.9 mmol) and methanol (10 ml) were reacted by microwave heating to 65 C for 10 min to afford methyl 3- (benzylamino) propionoate, which was purified by column chromatography on silica, eluting with hexane-ethyl acetate (8:2). Yield: 5.30 g, 82 %. 1 H-NMR (200 MHz, CDCl 3, 20 ºC, TMS): = 1.82 (br s, 1H, CH 2 -NH-CH 2 ), 2.54 (t, J = 6.6 Hz, 2H, CH 2 -CH 2 -COO ), 2.89 (t, J = 6.4 Hz, 2H, CH 2 -CH 2 -COO), 3.67 (s, 3H, OCH 3 ), 3.80 (s, 2H, C 6 H 5 -CH 2 ), (m, 5H, C 6 H 5 ) ppm. 13 C-NMR (50 MHz, CDCl 3, 20 ºC, TMS): = 34.7 (CH 2 -CH 2 -COO), 44.6 (CH 2 -CH 2 -COO), 51.8 (C 6 H 5 -CH 2 -N), 53.9 (OCH 3 ), 127.0, 128.1, (o-c 6 H 5, m-c 6 H 5, p- C 6 H 5 ), (i-c 6 H 5 ), (COO) ppm. Methyl 3-(benzylamino) propionoate (5.60 g, 29 mmol) was hydrolyzed with NaOH (2.60 g, 65 mmol) in MeOH/THF (10 ml) by microwave heating to 75 ºC for 1 h (according to TLC). After evaporation of the solvent under reduced pressure, the residue was acidified with aqueous 1N HCl until the solution reached ph 2. The resulting chlorohydrate was passed through an ion-exchange resin column (DOWEX-50WX8-200) to afford L2 as a white solid. Yield: 4.40 g, 84 %. Mp: ºC. 1 H-NMR (400 MHz, D 2 O, 20 ºC): = 2.48 (t, J = 6.8 Hz, 2H, CH 2 -CH 2 -COO), 3.12 (t, J = 7 Hz, 2H, CH 2 -CH 2 -COO), 4.14 (s, 2H, C 6 H 5 -CH 2 -N), (m, 5H, C 6 H 5 ) ppm. 13 C-NMR (100 MHz, D 2 O, 20 ºC): = 32.5 (CH 2 -CH 2 -COO), 43.9 (CH 2 -CH 2 -COO), 50.8 (C 6 H 5 -CH 2 ), 129.3, 129.6, (o-c 6 H 5, m-c 6 H 5, p-c 6 H 5 ), (i-c 6 H 5 ), (COO) ppm. 4-(benzylamino)butyric acid L3 To a solution of 4-aminobutyric acid (1.00 g, 9.7 mmol) in MeOH (15 ml) at 0 ºC, SOCl 2 (1.70 g, 14.6 mmol) was added. After stirring the solution for 1.5 h, it was allowed to reach room temperature, whereupon the solvent was evaporated to obtain methyl 4-amino butyrate as yellow oil (1.13 g, quantitative, identified by 1 H NMR). The O-amino ester (1.13 g, 9.7 mmol) was dissolved in acetonitrile (25 ml) and benzyl bromide (3.70 g, 21.6 mmol) was added. After cooling the solution to 0 ºC and addition of Na 2 CO 3 (2.31 g, 22 mmol), the resultant mixture was stirred for 24 h at room temperature. Then, the solvent was evaporated and the reaction mixture extracted with ethyl acetate (3 x 15 ml). The organic phase was dried with MgSO 4 and evaporated under reduced pressure. The crude was purified by column S3

4 chromatography (hexane: ethyl acetate, 8:2 P 5:5) to produce methyl 4-(dibenzylamino) butyrate as a viscous yellow oil. Yield: 1.45 g, 50 %. 1 H-NMR (200 MHz, CD 3 OD, 20 ºC, TMS): = 1.76 (q, J = 7 Hz, 2H, CH 2 -CH 2 -CH 2 ), 2.27 (t, J = 7.1 Hz, 2H, CH 2 -CH 2 -COO), 2.38 (t, J = 6.8 Hz, 2H, N-CH 2 -CH 2 ), 3.48 (s, 4H, C 6 H 5 -CH 2 -N), 3.54 (s, 3H, OCH 3 ), (m, 10H, C 6 H 5 ) ppm. 13 C-NMR (50 MHz, CD 3 OD, 20 ºC, TMS): = 23.4 (CH 2 -CH 2 - CH 2 ), 32.5 (CH 2 -CH 2 -COO), 52.1, 53.4 (N-CH 2 -CH 2, OCH 3 ), 59.4 (C 6 H 5 -CH 2 -N), 128.0, 129.3, (o-c 6 H 5, m-c 6 H 5, p-c 6 H 5 ), (i-c 6 H 5 ), (COO) ppm. For the preparation of 4-(benzylamino)butyric acid L3, to a solution of methyl 4-(dibenzylamino) butyrate (1.90 g, 6.4 mmol) in MeOH/THF (20 ml), an aqueous solution of NaOH (0.90 g, 22.6 mmol) was added. The reaction mixture was microwave- heated to 65 ºC for 0.5 h. After evaporation of the solvent under reduced pressure, the residue was dissolved in H 2 O and acidified with aqueous 1N HCl until it reached ph 3. The acidic solution was then evaporated under vacuum and the residue was redissolved in MeOH, whereby insoluble salts were separated by filtration. After removal of the solvent by vaccum distillation, the monohydrogenolysis reaction was carried out without further purification. Pd/C catalyst (0.30 g, 15% w/w) and 2-3 drops of concentrated HCl were added, and then the reaction mixture was stirred and pressurized with H 2 (60 lb) for 2h. After filtration of the mixture and concentration under reduced pressure, the crude product was passed through an ion-exchange resin column (DOWEX-50WX8-200) to afford 4-(benzylamino)butyric acid L3 as white solid. Yield: 0.95 g, 77 %. Mp: ºC. 1 H-NMR (400 MHz, CD 3 OD, 20 ºC, TMS): = 1.88 (q, J = 6.4 Hz, 2H, CH 2 -CH 2 -CH 2 ), 2.35 (t, J = 6.6 Hz, 2H, CH 2 -CH 2 -COO), 3.06 (t, J = 6.4 Hz, 2H, NH 2 -CH 2 -CH 2 ), 4.14 (s, 2H, C 6 H 5 -CH 2 -NH), (m, 5H, C 6 H 5 ) ppm. 13 C NMR (100 MHz, CD 3 OD, 20 ºC, TMS): = 23.6 (CH 2 -CH 2 -CH 2 ), 37.2 (CH 2 -CH 2 -COO), 49.3 (N-CH 2 -CH 2 ), 52.1 (Ph-CH 2 -N), 130.2, 130.4, (o-c 6 H 5, p-c 6 H 5, m- C 6 H 5 ), (i- C 6 H 5 ), (COO) ppm. S4

5 O OMe BnNH 2 µw, 65ºC, 3 min MeOH N H O OMe NaOH µw, 65ºC, 0.5h MeOH/THF O N H OH L2 Scheme S1. Synthesis of 3-(benzylamino)propionic acid L2. H 2 N O OH 1. SOCl 2 /MeOH 2. BnBr, Na 2 CO 3 MeCN N 2 O OMe 1. NaOH, µw MeOH/THF 2. H 2, Pd/C, HCl MeOH N H O OH Scheme S2. Reaction sequence for the benzylation of 4-aminobutyric acid. L3 S5

6 a) Vibrational spectrum IR intensity ,000 1,500 Frequency, cm**-1 2,000 2,500 3,000 b) Figure S1. Calculated (B3LYP/SBKJC(d,p)) and experimental (KBr) IR spectra for compound 5. S6

7 Figure S2: Perspective view of the supramolecular synthon (a) in the crystal structure of compound 6 that gives rise to 1 1D molecular arrangement (b). S7

8 Figure S3. Changes of the absortion spectra during the titration of 7 (6.7 x 10-5 M) with different quantities of AcOTBA (0-3.6 x10-2 M) in CHCl 3. The arrows indicate the spectral changes occurring in response to an increasing concentration of AcOTBA. Figure S4. Plots for the titration of compounds 8 and 9 with AcOTBA in CHCl 3. S8

9 Figure S Sn NMR spectra before and after addition of AcOTBA for compounds a) 6 and b) 7. Figure S6. Complexation induced shifts (CIS) for the 1 H NMR signals of the N-CH 2 -spacer (left) and CH 2 -COO groups (right) in compound 6 upon addition of AcOTBA in a solution in CDCl 3 at 25 o C. The solid curve is fitting to a 1:1 binding model from which K as was calculated. S9

10 Table S4. Atomic coordinates and selected geometric parameters for the calculated molecular structure of compound 5 (B3LYP/SBKJC(d,p)). Sn Sn S S S S N N O O O O C C C C C C C C C C C C C C C C C C C C C C C C C C C C H H H H H H H H S10

11 H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H S11

12 Table S4 (cont.). Selected bond lengths and angles for compound 5 Bond lengths (Å) Sn1-S O2-C Sn1-S C2-C Sn1-O C3-C Sn1-O C4-C Sn1-C C6-C Sn1-C C7-C S1-C C7-C S2-C C8-C N1-C C9-C N1-C C10-C N1-C C11-C O1-C Angles ( ) S1-Sn1-S C1-N1-C S1-Sn1-O C2-N1-C S1-Sn1-C N1-C2-C S1-Sn1-C N1-C6-C Sn1-S1-C O1-C5-O S2-Sn1-O O1-C5-C S2-Sn1-C C3-C2-C S2-Sn1-C C3-C4-C Sn1-S2-C C6-C7-C O1-Sn1-C C6-C7-C O1-Sn1-C C8-C7-C Sn1-O1-C C7-C8-C C14-Sn1-C C7-C12-C S1-C1-S C8-C9-C S1-C1-C C9-C10-C S2-C1-N C10-C11-C C1-N1C S12

13 Table S2. Calculated and experimental vibrational frequencies for [Me 2 Sn(L3-dtc)] 3 (5). Vibration B3LYP/ SKBCJ(d,p) IR data as (OCO) (N-CSS) s (OCO) s (N-C alkyl ) + s (SCS) as (N-C alkyl ) + as (SCS) as (SCS) (Sn-C-H) (Sn-O) a s (SCS) a s (Sn-C) a (Sn-S) a a) Could not be assigned unequivocally (several bands are present in this region). Table S3. Selected NMR spectroscopic data for compounds L1HCl, L2, L3 and 1-7 (in CDCl 3, ppm). 1 H NMR 1 H NMR 1 H NMR 13 C NMR 13 C NMR 13 C NMR 13 C NMR 13 C NMR 119 Sn NMR Compound (N-CH 2- spacer) (N-CH 2- Ph) (CH 2- COO) ( N-CH 2- spacer) ( N-CH 2- Ph) (CH 2- COO) (COO) (CSS) L1HCl a L2 a L3 b a) in D 2 O; b) in CD 3 OD S13

14 Table S4. Atomic coordinates and selected geometric parameters for the calculated molecular structure of compound 1 (B3LYP/SBKJC(d,p)). C C C C C C C C C C C C C C C C C C C C C N N N C C C C C C O O O O O O C C C S S S S S S H H S14

15 H H H H H H H H H H H H H H H H H H H H H H H H H Sn Sn Sn C C C H H H H H H H H H C C C H H H H H H H H S15

16 H Table S4 (cont.). Selected bond lengths and angles for compound 1 Bond lengths (Å) C11-C C3-O C7-C C3-O C10-C C1-S C9-C C1-S C9-C Sn1-S C7-C Sn1-S C6-C Sn1-C N1-C Sn1-C N1-C Sn1-O C2-C Angles ( ) C7-C11-C C2-C3-O C10-C11-C C2-C3-O C8-C7-C O2-C3-O C12-C7-C C3-Sn1-S C11-C10-C S1-C1-S C10-C9-C C1-S1-Sn C9-C8-C C1-S2-Sn C8-C7-C S1-Sn1-S C7-C6-N S1-Sn1-C C6-N1-C S1-Sn1-C N1-C2-C S2-Sn1-C C2-N1-C S2-Sn1-C N1-C1-S C14-Sn1-C N1-C1-S S16

Supporting Information

Electronic Supplementary Material (ESI) for RSC Advances. This journal is The Royal Society of Chemistry 2016 Supporting Information TEMPO-catalyzed Synthesis of 5-Substituted Isoxazoles from Propargylic