Switching from (R)- to (S)-selective chemoenzymatic DKR of amines involving sulfanyl radical-mediated racemization
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1 Switching from (R)- to (S)-selective chemoenzymatic DKR of amines involving sulfanyl radical-mediated racemization Lahssen El Blidi, b Nicolas Vanthuyne, b Didier Siri, c Stéphane Gastaldi,* a Michèle P. Bertrand* a and Gérard Gil* b a Equipe Chimie Moléculaire rganique, LCP UMR 6264,Boite 562, Université Paul Cézanne, Faculté des Sciences St Jérôme, Avenue Escadrille Normandie-Niemen, Marseille Cedex 20 (France). michele.bertrand@univ-cezanne.fr b Chirosciences, ISM2, UMR 6263, Université Paul Cézanne, Faculté des Sciences St Jérôme, Avenue Escadrille Normandie-Niemen, Marseille Cedex 20 (France). c Equipe Chimie Théorique et Modélisation Moléculaire, LCP UMR 6264, Université de Provence, Faculté des Sciences St Jérôme, Avenue Escadrille Normandie-Niemen, Marseille Cedex 20 (France) Electronic Supplementary Information Table of contents - Experimental procedures.. S1 - NMR spectra for compounds A, 2d, 2f, 4, 5a-g... S10-S36 - G3B3(MP2) calculations of SH BDE in trifluoro ethane thiol; capto-dative CH BDEs in N- acetylglycine ethyl and trifluoroethyl esters, N-acetyl alanine ethyl and trifluoroethyl ester and corresponding N-i-propylamides...S37 Experimental Section General : The 1 H and 13 C NMR spectra were recorded at 200, 300 or 400 MHz and 50, 75 or 100 MHz, respectively. Chemical shifts ( ) are reported in ppm and coupling constants (J) are given in Hz. Enantiomeric excesses (ee) of amides were determined by analytical chiral S 1
2 HPLC. The solvents for chiral chromatography (n-hexane, 2-PrH, EtH) were HPLC grade. They were degassed and filtered on a 0.45 µm membrane before use. The chiral HPLC analyses were performed on Chiralcel D-H (250*4.6mm, cellulose tris-(3,5- dimethylphenylcarbamate)), Chiralpak AD (250*4.6mm, amylose tris-(3,5- dimethylphenylcarbamate)), Chiralpak IC (250*4.6mm, cellulose tris(3,5- dichlorophenylcarbamate)), Ulmo (S,S) (250*4.6mm, silica bound N-(11- dimethylchlorosilyl)undecanoyl-n -3,5-dinitrobenzoyl-(1S,2S)-diphenylethanediamine), with UV detection. The retention times t R are given in minutes for each enantiomer, the retention factors k = (t R -t 0 )/t 0 (t 0 is the retention time for an unretained peak determined by injection of tri-tertiobutyl-benzene), the selectivity factor = k 2 /k 1, and the resolution Rs are given to characterize the separations. The enantiomeric excesses of the primary amine were determined, after derivatization in trifluoroacetamide with 1.5 equiv of N-methyl-bistrifluoroacetamide, by gas chromatography (GC) analysis on a chromatograph fitted with a Lipodex D column with flame ionization detector (FID), using the derivatized racemic compounds as reference. Trifluoroethane thiol, amines (2a, 2b, 2c, 2e and 2g) and enzymes (Protex 50FP, Alkaline protease) are commercially available. They were used without further purification. Compounds 2d 1 and 2f 2 were prepared according to literature procedures. The assay method used by Valley Research for the determination of enzymatic activities was based on the proteolytic hydrolysis of casein. The Alkaline Protease from Bacillus licheniformis has an enzymatic activity of 1660 DAPU/g. The specific assay methods are available from this company upon request. Immobilization of Protex 50FP 3 In a 50 ml flask, Protex 50FP crystalline form (80 mg) from Genencor was dissolved in a solution of n-octyl α,β-d-glycopyranoside (15 mg) and Brij 56 (polyethylene glycol hexadecyl S 2
3 ether, 15 mg) in a phosphate buffer (ph 7.2, 6 ml) and the mixture was rapidly frozen in liquid N 2 and lyophilized for 24 hours. Immobilization of alkaline protease In a 100 ml flask, 60 mg of octyl α,β-d-glycopyranoside and 60 mg of methyl-β-cyclodextrin were diluted at 60 C in 50 ml of buffer (Phosphate 0.1M, ph 7), this solution was then cooled to RT. The alkaline protease liquid extract (500 mg) from Valley Research was added to 25 ml of the previous solution. The mixture was rapidly frozen in liquid N 2 and lyophilized for 20 hours to give 822 mg of enzymatic powder. N-ctanoyl L-alanine trifluoroethyl ester (4). L-Alanine n-c 7 H 15 -CCl 92% C 7 H 15 A N H H BF 3. Et 2 CF 3 CH 2 H 74% CF C 7 H 15 N 3 H 4 N-ctanoyl L-alanine (A). To a solution of L-alanine (100 mmol, 8.9 g) in a 15% NaH (50 ml), at 0 C was added octanoyl chloride (1.5 equiv, 13.3 ml). The reaction mixture was stirred overnight at RT. After adding 20% HCl to ph 2, the organic products were extracted with dichloromethane (2 x 50 ml). The solvent was evaporated and the residue was purified by recrystallization from a chloroform/hexane mixture. Compound A (19.9 g, 92.4 mmol, 92%) was obtained as a white powder. 1 H NMR (200 MHz, CDCl 3 ): 0.87 (m, 3H), 1.27 (m, 8H), 1.45 (d, J = 7.0, 3H), 1.63 (m, 2H), 2.21 (t, J = 7.0, 2H), 4.58 (pseudo quint, J = 6.7, 1H), 6.23 (d, J = 5.8, 1H, NH), 7.45 (s, 1H, CH). 13 C NMR (75 MHz, CDCl 3 ): 14.1 (CH 3 ), 18.2 (CH 3 ), 22.6 (CH 2 ), 25.7 (CH 2 ), 29.0 (CH 2 ), 29.2 (CH 2 ), 31.7 (CH 2 ), 36.4 (CH 2 ), 48.3 (CH), (C), (C). m.p C. HRMS ([M+H] +, ESI): m/z calcd for: C 11 H 22 N 3 : Found: [a] D = +5.8 (c = 1.00 in CHCl 3 ). S 3
4 N-ctanoyl L-alanine trifluoroethyl ester (4). After dilution of A (20 mmol, 4.3 g) in trifluoroethanol (1.5 mol, 109 ml), BF 3 Et 2 (150 μl) were added at 0 C. The reaction mixture was refluxed for 8 days. After distillation of trifluoroethanol, the mixture was diluted in dichloromethane (50 ml) and washed successively with 1N HCl, 1N NaH, and brine. After evaporation of the solvent, 4 (4.4 g, 14 mmol, 74 %) was obtained as a white powder. 1 H NMR (200 MHz, CDCl 3 ): 0.84 (t, J = 6.4, 3H), 1.27 (m, 8H), 1.45 (d, J = 7.2, 3H), 1.62 (quint, J = 7.2, 2H), 2.21 (t, J = 7.2, 2H), (AB part of an ABX 3 pattern, 2H), 4.62 (superimposed m, 1H), 5.99 (d, J = 6.6, 1H NH). 13 C NMR (50 MHz, CDCl 3 ): 14.1 (CH 3 ), 18.1 (CH 3 ), 22.7 (CH 2 ), 25.6 (CH 2 ), 29.0 (CH 2 ), 29.2 (CH 2 ), 31.7 (CH 2 ), 36.4 (CH 2 ), 47.8 (CH), 60.5 (CH 2, q, 2 J CF = 37), (CF 3, q, 1 J CF = 279), (C), (C). m.p C. Ee > 99.5% (chiral HPLC, chiralcel D-H, n-hexane/ethanol 98:2, flow rate = 1 ml/min, UV 220 nm, t R (R) = 14.2 min, t R (S) = 17.3 min, k(r) = 3.66, k(s) = 4.67, α = 1.28, Rs = 1.8. [a] D 25 = -7.5 (c = 1.03 in CHCl 3 ). HRMS ([M+H] +, ESI): m/z calcd for: C 13 H 23 N 3 F 3 : Found: General Procedure for the synthesis of analytical samples of (S, R)- and (S, S)-amides (5a-g) for chiral HPLC analysis : NH 2 R racemic + CF C 7 H 15 N 3 H 4 H coated Protex 50FP (S) N C 7 H 15 HN + t-buh R (S) H (S) N C 7 H 15 HN R (R) To a solution of 4 (0.25 mmol) and amines (2) (0.25 mmol) in t-buh (0.5 M) was added 25 mg of non-stereoselective coated enzyme Protex 50FP. The resulting mixture was stirred at room temperature (24-72h). After filtration of the enzyme and concentration, the product was purified by chromatography on gel-silica (dichloromethane/meh 0 to 5%). S 4
5 For each couple of (S,R)- and (S,S)-amides, the 1/1 ratio of the mixture was checked by NMR. This 1/1 ratio was also obtained by integration of the UV chiral HPLC chromatogram, showing that (S,R)- and (S,S)-amides have the same UV extiction coefficient at the wavelength used for the analysis. General Procedure for the kinetic resolution of amines: To a solution of acyl donor (4) (104 mg, 0.35 mmol) in t-buh (5 ml) was added coated alkaline protease (25 mg) and amine (2) (0.5 mmol). The resulting mixture was stirred at room temperature for 60 minutes. The amine ee was determined by GC after derivatization of an aliquot of the crude mixture in trifluoroacetamide with 1.5 equiv of N-methyl-bis-trifluoroacetamide. The enzyme was filtered off from the solution and washed with dichloromethane (10 ml). Then Boc 2 (66 mg, 0.3 mmol) was added to the filtrate, and the mixture was stirred until complete consumption of the amine (TLC monitoring). The solvent was then evaporated and the crude mixture was purified on gel-silica (pentane/diethyl ether 0 to 10% to afford the Boc-amine, then dichloromethane/meh 0 to 1% to afford the amide). General Procedure for the dynamic kinetic resolution of amines: To a solution of N- octanoyl-l-alanine trifluoroethyl ester (4) (125 mg, 0.42 mmol) in t-buh/thf:5/1 (3 ml, 0.1 M) was added coated alkaline protease (15 mg) and the amine (0.3 mmol). The mixture was irradiated at C in a quartz tube (diameter 1.5 cm) in a Rayonet apparatus (RPR- 200, 16 UV lamps Sylvania Blacklight 351 F15W/T5/BL350) for 2h30 and AIBN (45 mg, 0.25 mmol) was added by portion every 45 min (3 x 15 mg). The enzyme was filtered off from the solution and washed with dichloromethane (5 ml). The solvent was then evaporated and the crude material was purified by flash column chromatography on silica gel (dichloromethane/methanol 0 to 5%) to give pure amide. N-((S)-1-((S)-4-phenylbutan-2-ylcarbamoyl)ethyl)octanamide (5a): S 5
6 Ph H (S) N C 7 H 15 HN (S) Prepared in 78% yield from amine 2a according to the general procedure for dynamic kinetic resolutions. 1 H NMR (400 MHz, CDCl 3 ): 0.88 (t, J = 6.5, 3H), 1.17 (d, J = 7.0, 3H), (m, 8H), 1.39 (d, J = 7.0, 3H), 1.60 (pseudo quint, J = 7.0, 2H), 1.77 (m, 2H), 2.17 (m, 2H), 2.63 (m, 2H), 3.98 (sept, J = 7.0, 1H), 4.57 (quint, J = 7.0, 1H), 6.21 (d, J = 6.5, 1H, NH), 6.32 (d, J = 8.0, 1H, NH), (m, 5H). 13 C NMR (100 MHz, CDCl 3 ): 14.1 (CH 3 ), 19.1 (CH 3 ), 20.9 (CH 3 ), 22.6 (CH 2 ), 25.7 (CH 2 ), 29.0 (CH 2 ), 29.2 (CH 2 ), 31.7 (CH 2 ), 32.5 (CH 2 ), 36.6 (CH 2 ), 38.6 (CH 2 ), 45.1 (CH), 48.8 (CH), (CH), (2xCH), (2xCH), (C), (C), (C). HPLC conditions: Chiralcel D-H, n-hexane/ethanol 98:2, flow rate = 1 ml/min, UV 254 nm, t R (S,S) = 10.8 min, t R (S,R) = 12.7 min, k(s,r) = , k(s,s) = 3.16, α = 1.24, Rs = 1.3. Diastereomeric excess 93%. [a] D = (c = 1.00 in CHCl 3 ). HRMS ([M+H] +, ESI): m/z calcd for: C 21 H 35 N 2 2 : Found: N-((S)-1-((S)-heptan-2-ylcarbamoyl)ethyl)octanamide (5b): H (S) N C 7 H 15 HN (S) Prepared in 68% yield from amine 2b according to the general procedure for dynamic kinetic resolutions. 1 H NMR (400 MHz, CDCl 3 ): 0.87 (t, J = 6.5, 6H), 1.10 (d, J = 6.5, 3H), (m, 14H), 1.36 (d, J = 7.0, 3H), 1.42 (m, 2H), 1.61 (quint, J = 7.0, 2H), 2.18 (broad t, J = 7.3, 2H), 3.90 (sept, J = 6.5, 1H), 4.51 (quint, J = 7.0, 1H), 6.45 (m, 2H, NH). 13 C NMR (100 MHz, CDCl 3 ): 14.0 (CH 3 ), 14.0 (CH 3 ), 18.9 (CH 3 ), 20.8 (CH 3 ), 22.5 (CH 2 ), 22.6 (CH 2 ), 25.6 (CH 2 ), 25.7 (CH 2 ), 29.0 (CH 2 ), 29.2 (CH 2 ), 31.6 (CH 2 ), 31.7 (CH 2 ), 36.6 (CH 2 ), 36.7 (CH 2 ), 45.4 (CH), 48.8 (CH), (C), (C). m.p C. HPLC conditions: Chiralpak IC, n-hexane/isopropanol: 95/5, flow rate = 1 ml/min, UV 210 nm, t R (S,R) = 7.02; t R (S,S) = 7.72, k(s,r) = 1.34, k(s,s) = 1.57, α = 1.17, Rs = Diastereomeric excess 92%. [α] 25 D = - S 6
7 40.2 (c 0.55, CHCl 3 ). HRMS ([M+H] +, ESI): m/z calcd for: C 18 H 37 N 2 2 : Found: N-((S)-1-((S)-6-methylheptan-2-ylcarbamoyl)ethyl)octanamide (5c): H (S) N C 7 H 15 HN (S) Prepared in 73% yield from amine 2c according to the general procedure for dynamic kinetic resolutions. 1 H NMR (400 MHz, CDCl 3 ): 0.86 (d, J = 6.5, 6H), 0.88 (t, J = 6.5, 3H), 1.10 (d, J = 6.5, 3H), (m, 2H), (m, 11H), 1.37 (d, J = 7.0, 3H), (m, 2H), 1.51 (sept, J = 6.5, 1H), 1.61 (quint, J = 7.3, 1H), 2.19 (broad t, J = 7.3, 2H), 3.92 (hept, J = 6.5, 1H), 4.53 (quint, J = 7.0, 1H), 6.48 (d, J = 7.0, 1H, NH), 6.63 (d, J = 8.0, 1H, NH). 13 C NMR (100 MHz, CDCl 3 ): 14.0 (CH 3 ), 19.0 (CH 3 ), 19.5 (CH 3 ), 20.8 (CH 3 ), 22.5 (CH 3 ), 22.6 (CH 2 ), 23.8 (CH 2 ), 25.7 (CH 2 ), 27.8 (CH), 29.0 (CH 2 ), 29.2 (CH 2 ), 31.7 (CH 2 ), 36.6 (CH 2 ), 37.0 (CH 2 ); 38.7 (CH 2 ), 45.3 (CH), 48.8 (CH), (C), (C). m.p C. HPLC conditions: Chiralpak IC, n-hexane/isopropanol: 95/5, flow rate = 1 ml/min, UV 210 nm, t R (S,R) = 7.96; t R (S,S) = 9.27, k(s,r) = 1.65, k(s,s) = 2.09, α = 1.26, Rs = Diastereomeric excess 88%. [α] 25 D = (c 0.77, CHCl 3 ). HRMS ([M+H] +, ESI): m/z calcd for: C 19 H 39 N 2 2 : Found: N-((S)-1-((S)-6-methylhept-5-en-2-ylcarbamoyl)ethyl)octanamide (5d): H (S) N C 7 H 15 HN (S) Prepared in 66% yield from amine 2d according to the general procedure for dynamic kinetic resolutions. 1 H NMR (400 MHz, CDCl 3 ): 0.87 (t, J = 6.8, 3H), 1.12 (d, J = 6.8, 3H), (m, 8H), 1.37 (d, J = 7.0, 3H), 1.47 (pseudo q, J = 7.2, 3H), 1.59 (s, 3H), 1.62 (quint, J = 7.3, 2H), 1.69 (s, 3H), 2.0 (broad q, J = 7.3, 2H), 2.19 (broad t, J = 6.9, 2H), 3.93 (sept, J = 6.5, 1H), 4.47 (quint, J = 7.0, 1H), 5.09 (broad t, J = 7.3, 1H), 6.23 (broad s, 2H, NH). 13 C NMR S 7
8 (100 MHz, CDCl 3 ): 14.0 (CH 3 ), 17.6 (CH 3 ), 19.0 (CH 3 ), 20.8 ( CH 3 ), 22.6 (CH 2 ), 24.6 (CH 2 ), 25.6 (CH 2 ), 25.7 (CH 3 ), 29.0 (CH 2 ), 29.2 (CH 2 ), 31.7 (CH 2 ), 36.6 (CH 2 ); 36.8 (CH 2 ), 45.1 (CH), 48.8 (CH), (CH), (C), (C), (C). m.p C. HPLC conditions: Chiralcel D-H, n-hexane/isopropanol: 99/1, flow rate = 1 ml/min, UV 220 nm, t R (S,S) = 13.2, t R (S,R) = 18.05, k(s,s) = 3.40, k(s,r) = 5.02, α = Diastereomeric excess 90%. [α] 25 D = (c 0.91, CHCl 3 ). HRMS ([M+H] +, ESI): m/z calcd for: C 19 H 37 N 2 2 : Found: N-((S)-1-((S)-6-hydroxy-6-methylheptan-2-ylcarbamoyl)ethyl)octanamide (5e): H H (S) N C 7 H 15 HN (S) Prepared in 72% yield from amine 5e according to the general procedure for dynamic kinetic resolutions. 1 H NMR (400 MHz, CDCl 3 ): 0.86 (t, J = 6.5, 3H), 1.11 (d, J = 6.6, 3H), 1.17 (s, 3H), 1.19 (s, 3H), (m, 8H), 1.35 (d, J = 7.0, 3H), (m, 6H), 1.60 (pseudo quint, J = 7.0, 2H), 2.04 (broad s, 1H), 2.17 (broad t, J = 8.3, 2H), 3.95 (sept, J = 6.6, 1H), 4.49 (quint, J = 7.0, 1H), 6.44 (d, J = 7.5, 1H, NH), 6.63 (d, J = 8.5, 1H, NH). 13 C NMR (100 MHz, CDCl 3 ): 14.0 (CH 3 ), 18.8 (CH 3 ), 20.6 (CH 2 ), 20.9 (CH 3 ), 22.6 (CH 2 ), 25.7 (CH 2 ), 28.9 (CH 2 ), 29.0 (CH 3 ), 29.2 (CH 2 ), 29.5 (CH 3 ), 31.7 (CH 2 ), 36.6 (CH 2 ), 37.2 (CH 2 ), 43.3 (CH 2 ), 45.0 (CH), 48.8 (CH), 70.7 (C), (C), (C). m.p C. HPLC conditions: Ulmo (S, S), n-hexane/isopropanol: 95/5, flow rate = 1 ml/min, UV 220 nm, t R (S,S) = 7.22, t R (S,R) = 10.97, k(s,s) = 1.42, k(s,r) = 2.66, α = 1.89, Rs = Diastereomeric excess 78%. [α] 25 D = (c 0.67, CHCl 3 ). HRMS ([M+H] +, ESI): m/z calcd for: C 19 H 39 N 2 3 : Found: N-((S)-1-((S)-4-(octylthio)butan-2-ylcarbamoyl)ethyl)octanamide (5f): S H (S) N C 7 H 15 HN (S) S 8
9 Prepared in 68% yield from amine 5f according to the general procedure for dynamic kinetic resolutions. 1 H NMR (400 MHz, CDCl 3 ): 0.88 (t, J = 6.5, 6H), 1.14 (d, J = 6.8, 3H), (m, 18H), 1.36 (d, J = 7.0, 3H), (m, 4H), 1.74 (m, 2H), 2.1 (broad t, J = 7.5, 2H), 2.5 (m, 4H), 4.05 (m, 1H), 4.55 (quint, J = 7.0, 1H), 6.40 (broad s, 1H, NH), 6.72 (broad s, 1H, NH). 13 C NMR (100 MHz, CDCl 3 ): 14.0 (CH 3 ), 14.1 (CH 3 ), 18.9 (CH 3 ), 20.7 (CH 3 ), 22.6 (CH 2 ), 22.6 (CH 2 ), 25.6 (CH 2 ), 28.6 (CH 2 ), 28.9 (CH 2 ), 29.0 (CH 2 ), 29.1 (CH 2 ), 29.2 (CH 2 ), 29.2 (CH 2 ), 29.6 (CH 2 ), 31.7 (CH 2 ), 31.8 (CH 2 ), 32.3 (CH 2 ), 36.6 (CH 2 ), 36.7 (CH 2 ), 44.9 (CH), 48.8 (CH), (C), (C). m.p C. HPLC conditions: Chiralpak AD, n- hexane/isopropanol: 95/5, flow rate = 1 ml/min, UV 220 nm, t R (S,R) = 5.30, t R (S,S) = 7.02, k(s,r) = 0.77, k(s,s) = 1.34, α = Diastereomeric excess 88%. [α] 25 D = (c 0.85, CHCl 3 ). HRMS ([M+H] +, ESI): m/z calcd for: C 23 H 47 N 2 2 S: Found: N-((S)-1-((S)-4-methoxy-4-oxo-butan-2-ylcarbamoyl)ethyl)octanamide (5g): H (S) N C 7 H 15 HN (S) Prepared in 65% yield from amine 5g according to the general procedure for dynamic kinetic resolutions. 1 H NMR (300MHz, CDCl 3 ): 0.88 (t, J = 6.5, 3H), 1.21 (d, J = 6.8, 3H), (m, 9H), 1.33 (d, J = 6.9, 3H), 1.61 (pseudo quint, J = 6.6, 2H), 2.19 (t, J = 7.3, 2H), 2.52 (d, J = 5.6, 2H), 3.68 (s, 3H), 4.05 (sept, J = 6.4, 1H), 4.48 (quint, J = 6.9, 1H), 6.35 (broad s, 1H, NH), 6.92 (broad s, 1H, NH). 13 C NMR (50 MHz, CDCl 3 ): 14.4 (CH 3 ), 19.2 (CH 3 ), 20.4 (CH 3 ), 22.9 (CH 2 ), 26.0 (CH 2 ), 29.4 (CH 2 ), 29.6 (CH 2 ), 32.0 (CH 2 ), 37.0 (CH 2 ), 40.5 (CH 2 ), 42.7 (CH), 49.1 (CH), 52.0 (CH 3 ), (C), (C), (C). HPLC conditions: Chiralcel J-H, n-hexane/isopropanol: 95/5, flow rate = 1 ml/min, UV 220 nm, t R (S,R) = 6.51, t R (S,S) = 7.52, k(s,r) = 1.17, k(s,s) = 1.51, α = 1.29, Rs = Diastereomeric excess 73%. [α] 25 D = +6.2 (c 0.48, CHCl 3 ). HRMS ([M+H] +, ESI): m/z calcd for: C 16 H 31 N 2 4 : Found: S 9
10 6-Methylhept-5-en-2-amine (2d): 1 H NMR S 10
11 6-Methylhept-5-en-2-amine (2d): 13 C NMR S 11
12 6-Methylhept-5-en-2-amine (2d): DEPT S 12
13 (S)-4-(octylthio)butan-2-amine (2f): 1 H NMR S 13
14 (S)-4-(octylthio)butan-2-amine (2f): 13 C NMR S 14
15 (S)-4-(octylthio)butan-2-amine (2f): DEPT 135 S 15
16 N-ctanoyl L-alanine (A): 1 H NMR S 16
17 N-ctanoyl L-alanine (A): 13 C NMR S 17
18 N-ctanoyl L-alanine (A): DEPT S 18
19 N-ctanoyl L-alanine trifluoroethyl ester (4): 1 H NMR S 19
20 N-ctanoyl L-alanine trifluoroethyl ester (4): 13 C NMR S 20
21 N-ctanoyl L-alanine trifluoroethyl ester (4): DEPT S 21
22 N-((S)-1-((S)-4-phenylbutan-2-ylcarbamoyl)ethyl)octanamide (5a): 1 H NMR S 22
23 N-((S)-1-((S)-4-phenylbutan-2-ylcarbamoyl)ethyl)octanamide (5a): APT S 23
24 N-((S)-1-((S)-heptan-2-ylcarbamoyl)ethyl)octanamide (5b): 1 H NMR S 24
25 N-((S)-1-((S)-heptan-2-ylcarbamoyl)ethyl)octanamide (5b): APT S 25
26 N-((S)-1-((S)-6-methylheptan-2-ylcarbamoyl)ethyl)octanamide (5c): 1 H NMR S 26
27 N-((S)-1-((S)-6-methylheptan-2-ylcarbamoyl)ethyl)octanamide (5c): APT S 27
28 N-((S)-1-((S)-6-methylhept-5-en-2-ylcarbamoyl)ethyl)octanamide (5d): 1 H NMR S 28
29 N-((S)-1-((S)-6-methylhept-5-en-2-ylcarbamoyl)ethyl)octanamide (5d): APT S 29
30 N-((S)-1-((S)-6-hydroxy-6-methylheptan-2-ylcarbamoyl)ethyl)octanamide (5e): 1 H NMR S 30
31 N-((S)-1-((S)-6-hydroxy-6-methylheptan-2-ylcarbamoyl)ethyl)octanamide (5e): APT S 31
32 N-((S)-1-((S)-4-(octylthio)butan-2-ylcarbamoyl)ethyl)octanamide (5f): 1 H NMR S 32
33 N-((S)-1-((S)-4-(octylthio)butan-2-ylcarbamoyl)ethyl)octanamide (5f): APT S 33
34 N-((S)-1-((S)-4-methoxy-4-oxo-butan-2-ylcarbamoyl)ethyl)octanamide (5g): 1 H NMR S 34
35 N-((S)-1-((S)-4-methoxy-4-oxo-butan-2-ylcarbamoyl)ethyl)octanamide (5g): 13 C NMR S 35
36 N-((S)-1-((S)-4-methoxy-4-oxo-butan-2-ylcarbamoyl)ethyl)octanamide (5g): DEPT S 36
37 Computational details: G3B3(MP2) method was used to calculate the BDEs of both model compounds for the acyl donors, and the thiol, with the Gaussian 03 4 program. This method is well-known to provide accurate energies for radical intermediates. 5 G3B3(MP2) enthalpies at 298,15 K, C-H/S-H BDEs and cartesian coordinates are given in the following, for: ethyl esters of N- acetylglycine, N-acetylalanine, and the corresponding trifluoroethyl esters; for N- acetylalanine i-propyl amide, and all the corresponding carbon-centered radical species; for CF 3 CH 2 SH and the corresponding sulfanyl radical. The value for G3B3(MP2) enthalpy for H atom : au. N-acetylglycine ethyl ester G3B3(MP2) enthalpy = au. G3B3(MP2) C-H BDE = kj.mol -1 C H H C C C H H H H H N C H C H H H Corresponding Carbon-centered Radical S 37
38 G3B3(MP2) enthalpy = au. C H C C C H H H H H N C H C H H H N-acetylalanine ethyl ester G3B3(MP2) enthalpy = au. G3B3(MP2) C-H BDE = kj.mol -1 C H C C C H H H H H N C H C H H H C S 38
39 H H H Corresponding Carbon-centered Radical G3B3(MP2) enthalpy = au. C C C C H H H H H N C H C H H H C H H H N-acetylalanine i-propyl amide G3B3(MP2) enthalpy = au. G3B3(MP2) C-H BDE = kj.mol -1 C H C C S 39
40 C H H H H N C H C H H H C H H H N H C H H H Corresponding Carbon-centered Radical G3B3(MP2) enthalpy = au. C C C C H H H H N C H C H H H C H H H N S 40
41 H C H H H N-acetylglycine trifluoroethyl ester G3B3(MP2) enthalpy = au. G3B3(MP2) C-H BDE = kj.mol -1 C H H C C C H H N C H C H H H F F F Corresponding Carbon-centered Radical G3B3(MP2) enthalpy = au. C H C C C H S 41
42 H N C H C H H H F F F N-acetylalanine trifluoroethyl ester G3B3(MP2) enthalpy = au. G3B3(MP2) C-H BDE = kj.mol -1 C H C C C H H N C H C H H H F F F C H H H Corresponding Carbon-centered Radical S 42
43 G3B3(MP2) enthalpy = au. C C C C H H N C H C H H H F F F C H H H CF 3 CH 2 SH G3B3(MP2) enthalpy = au. G3B3(MP2) S-H BDE = kj.mol -1 C C H H S S 43
44 H F F F CF 3 CH 2 S G3B3(MP2) enthalpy = au. C C H H S F F F Escoubet, S.; Gastaldi, S.; Vanthuyne, N.; Gil, G.; Siri, D.; Bertrand, M. P. J. rg. Chem. 2006, 71, Routaboul, L.; Vanthuyne, N.; Gastaldi, S.; Gil, G.; Bertrand, M. P. J. rg. Chem. 2008, 73, Bottalla, A.-L.; Queyroy, S.; Azzi-Schue, N.; Vanthuyne, N.; Gastaldi, S.; Bertrand, M. P.; Gil, G. Tetrahedron: Asymmetry 2009, 20, Gaussian 09, Revision E.01, Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., S 44
45 Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao,., Nakai, H., Vreven, T., Montgomery, Jr., J. A., Peralta, J. E., gliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C. Iyengar, S. S. Tomasi, J. Cossi, M. Rega, Millam, N. J., Klene, M. Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R. E. Stratmann,. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. chterski, R. Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas,., Foresman, J. B., rtiz, J. V., Cioslowski, J., and Fox, D. J., Gaussian, Inc., Wallingford CT, Baboul, A. G.; Curtiss, L. A.; Redfern, P. C.; Raghavachari, K J. Chem. Phys. 1999, 110, S 45
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