ÐÏà¡±á>þÿ NPþÿÿÿMÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿÿì¥Á7 ð¿Ù=bjbjUU &^7|7|m5ÿÿÿÿÿÿlxxxxxxxŒÎÎÎ8LRŒ¶zz"œœœœœœ>@@@@@@$½ Ýšd]xœœœœœdDxxœœÁDDDœ¾ xœxœ>Dœ>DÖDxxœn€sowÔ*ÀŒBÎZê$×0wDwDŒŒxxxxÙSupporting Information Radical-Mediated Synthesis of C-Glycosides Based on N-Acyl Galactosamine Raul San Martin,a Bahareh Tavassoli,a Kenneth E. Walsh,a Daryl S. Walter,b and Timothy Gallaghera* aSchool of Chemistry, University of Bristol, Bristol BS8 1TS UK bRoche Discovery Welwyn, Broadwater Road, Welwyn Garden City AL7 3AY UK t.gallagher@bristol.ac.uk Where spectroscopic assignments have been made, these are based specifically on 1H-1H and 1H-13C correlation spectroscopy. It was interesting to note that the signal associated with C1 (in 13C NMR spectra) was consistently very weak in C-glycosides 7. Anomeric Selenides 5a: This compound has been reported previously. [Witczak, Z. Tetrahedron 1985, 41, 4781-478.]. 5b: 1H NMR (300 MHz, CDCl3) 7.62-7.54 (2 H, m), 7.38-7.28 (3 H, m), 7.09 (1 H, d, J 8.2 Hz, NH), 5.98 (1 H, d, J 4.9 Hz, H(1)), 5.52 (1 H, t, J 3.1 Hz, H(4)), 5.15 (1 H, d d, J 11.5, 3.1 Hz, H(3)), 4.72-4.68 (2 H, m, H(2), H(5)), 4.18 (1 H, d d J 11.5, 6.2 Hz, H(6), 4.10 (1 H, d d, J 11.5, 7.0 Hz, H(6)), 2.19 (3 H, s), 2.03, (3 H, s) and 1.96 (3 H, s); 13C NMR (75 MHz, CDCl3) 171.2, 170.3, 170.1, 164.0, 134.5, 129.5, 128.6, 127.4, 87.1, 69.9, 64.2, 66.7, 61.4, 49.7, 20.6, 20.5, 20.4 – CF3 was not observed); HRMS m/z calcd for C20H22F3NO874Se (M+) 535.0522, found 535.0506. 5c: 1H NMR (300 MHz, CDCl3) ) 7.63-7.57 (2 H, m), 7.34-7.25 (3 H, m), 6.01 (1 H, d, J 5 Hz, H(1)), 5.43 (1 H, br. d, J 2.0 Hz, H(4)), 4.95 (1 H, d d, J 11.1, 2.0 Hz, H(3)), 4.75 (1 H, d J 8.9 Hz, NH), 4.63 (1 H, t, J 6.2 Hz, H(5)), 4.44 (1 H, m, H(2)), 4.20-4.05 (2 H, m, H(6)), 2.16 (3 H, s), 2.03 (3 H, s), 2.02 (3 H, s), 1.65 (9 H, s); 13C NMR (75 MHz, CDCl3) 170.6, 170.3, 170.2, 155.0, 134.2, 129.2, 128.3, 128.0, 89.0 (C1), 80.2, 69.7 (broad, C3, C5), 67.1 (C4), 61.6 (C6), 50.1 (C2), 28.3, 20.7 (broad, two unresolved signals), 20.6; HRMS m/z calcd for C23H31NO974Se (M+) 539.1224, found 539.1202. Reduction products. 6a: IR (CHCl3) 3428, 1746, 1677 cm-1; 1H NMR (300 MHz, CDCl3) 5.78 (1 H, d, J 7.7 Hz, NH), 5.37 (1 H, d d, J 3.3, 1.1 Hz, H(4)), 4.95 (1 H, d d, J 11.2, 3.3Hz, H(3)), 4.42 (1 H, m, H(2)), 4.21 (1 H, d d, J 11.0, 5.1 Hz, H(1bð)), 4.15-4.03 (2 H, m, H(6)), 3.79 (1 H, t d, J 6.4, 1.1, H(5)), 3.18 (1 H, t, J 11.0, H(1að)ð), 2.16 (3 H, s), 2.06 (3 H, s), 2.04 (3 H, s), 1.97 (3 H, s); 13C NMR (75 MHz, CDCl3) 171.4, 170.5, 170.2, 75.0. 71.5 (C5), 68.5 (C3), 67.1 (C4), 62.2 (C6), 46.6 (C2), 23.2, 20.8, 20.7, 20.6 (one C=O signal was not resolved); HRMS m/z calcd for C14H22NO8 (MH+) 332.1345, found 332.1353. 6b: 1H NMR (300 MHz, CDCl3) 6.60 (1 H, d J 8.8 Hz, NH), 5.42 (1 H, d d , J 3.3, 1.1 Hz, H(4)), 5.03 (1 H, d d, J 11.0, 3.3 Hz, H(3)), 4.45 (1 H, m, H(2)), 4.26 (1 H, d d, J 11.1, 5.4 Hz, H(1bð)), 4.18-4.04 (2 H, m, H(6)), 3.82 (1 H, t d, J 6.3, 1.1 Hz, H(5)), 3.30 (1 H, t, J 11.1 Hz, H(1að)), 2.19 (3 H, s), 2.07 (3 H, s), 2.06 (3 H, s); 13C NMR (75 MHz, CDCl3) 171.7, 170.5, 170.1, 113.5, 75.3, 71.3, 67.7, 66.9, 62.0, 45.7, 20.8, 20.7, 20.6 CF3 was not observed; HRMS m/z calcd for C14H19F3NO8 (MH+) 386.1063, found 386.1068. 6c: 1H NMR (300 MHz, CDCl3) 5.38 (1 H, d d , J 3.3, 1.0 Hz, H(4)), 4.87 (1 H, d d, J 10.3, 3.3 Hz, H(3)), 4.44 (1H, d, J 8.4 Hz, NH), 4.21-4.02 (4 H, m, H1bð), H(2), 2xH(6)), 3.78 (1 H, t d, J 1.0, 6.4 Hz, H(5)), 3.21 (1 H, t , J 11 Hz, H(1að)ð)ð, 2.16 (3 H, s), 2.06 (3 H, s), 2.04 (3 H, s), 1.43 (9 H, s); 13C NMR (75 MHz, CDCl3) 171.6, 170.5, 169.8, 155.2, 80.0, 75.0 (C5), 71.9 (C3), 69.2 (C1), 67.2 (C4), 62.2 (C6), 45.9 (C2), 28.2, 20.7, 20.7, 20.6; HRMS m/z calcd for C17H27NO9 (M+) 389.1686, found 389.1710. Synthesis of C-Glycosides – Representative experimental procedures General procedure.- Alkene substrate (2.2 eq), purified and free from radical inhibitors, was added to a stirred solution of selenide 5 (1 eq) in freshly distilled toluene under nitrogen at room temperature. Tributyltin hydride (3.7 eq, as a freshly prepared 0.73 M solution in dry toluene) was added , followed immediately by triethyl borane (1 eq, as a 1 M solution in hexanes. The resulting solution was placed in an ultrasound bath and 0.02 mL of air was added by syringe. The solution was subjected to both sonication and irradiation using a 200 W (or 500 W) lamp until reaction was complete as judged by TLC. The reaction mixture was concentrated in vacuo and the residue was dissolved in acetonitrile (5 mL) and hexane (1 mL). The acetonitrile layer was separated, washed with hexane (6 ( 5 mL) and dried (Na2SO4), then filtered and concentrated in vacuo to give a oil, which was purified by flash column chromatography. Preparation of C-glycoside 7a Freshly distilled methyl acrylate (0.02 mL, 0.22 mmol, 2.2 eq) was added to a stirred solution of selenide 5a (50 mg, 0.1 mmol, 1 eq) in freshly distilled toluene under nitrogen at room temperature. Tributyltin hydride (0.51 mL of a freshly prepared 0.73 M solution in dry toluene, 0.37 mmol, 3.7 eq) was added, followed immediately by triethyl borane (0.1 mL of a 1 M solution in hexanes, 0.1 mmol, 1 eq). The resulting solution was placed in an ultrasound bath and 0.02 mL of air was added by syringe, and the solution was subjected to both sonication and irradiation using a 200 W lamp. After 1.5 hrs the reaction had gone to completion (as judged by TLC). The solution was concentrated in vacuo and the residue was dissolved in acetonitrile (5 mL) and hexane (1 mL). The acetonitile layer was separated, washed with hexane (6 ( 5 mL) and dried (Na2SO4), filtered and concentrated in vacuo to give an oil. Purification by flash column chromatography (silica gel 60, EtOAc as eluent), to give 7a (40 mg, 93 %) as a colorless oil. Preparation of styrene adduct 7b; isolation of reduction by-product 6a The same procedure was employed and after concentration in vacuo, the resulting oil was purified by flash column chromatography (silica gel 60H; 2:1 Petrol:EtOAc) to give 7b (18 mg, 37 %) as a colorless oil. Continued elution then gave the reduction product 6a (28 mg, 60 %) as a colorless foam. Characterization data for C-glycosides 7. 7a: 1H NMR (270 MHz, CDCl3) 6.06 (1 H, d, J 8.2 Hz, NH), 5.33 (1 H, t, J 3.3 Hz, H(4)), 5.15 (1 H, d d, J 10.2, 3.3 Hz, H(3)), 4.52 (1 H, m, H(2)), 4.29-4.15 (2 H, m, H(1), H(5)), 4.14-4.00 (2 H, m, 2xH(6)), 3.67 (3 H, s), 2.53-2.30 (2 H, m CH2CO2Me), 2.12 (3 H, s), 2.06 (6 H, br. s), 2.00 (3 H, s), 1.95 (1 H, m CHCHCH2CO2Me), 1.75 (1 H, m, CHCHCH2CO2Me); 1H NMR (300 MHz, CD3COCD3) 7.35 (1 H, d, J 8.1 Hz, NH), 5.36 (1 H, t, J 3.3 Hz, H(4)), 5.12 (1 H, d d, J 10.3, 3.3 Hz, H(3)), 4.60 (1 H, m, H(2)), 4.26-4.04 (4 H, m, H(1), H(5), 2xH(6)), 3.50 (3 H, s), 2.40-2.25 (2 H, m, CH2CO2Me), 2.09 (3 H, s), 2.07 (1 H, m, CHCHCH2CO2Me), 1.97 (3 H, s), 1.93 (3 H, s), 1.82 (3 H, s), 1.79 (1 H, m, CHCHCH2CO2Me); 13C NMR (75 MHz, CD3COCD3) 173.7, 170.4, 170.2, 170.1, 72.6 (C1), 69.1 (C5), 68.9 (C3), 67.8 (C4), 62.1 (C6), 51.5 (OMe), 48.7, 30.5, 22.6, 22.0, 20.6, 20.5 (broad, 2 unresolved peaks); HRMS m/z calcd for C18H28NO10 (MH+) 418.1713, found 418.1707. W½ of H(2) signal = 23.6 Hz (CDCl3); 23.5 Hz (CD3COCD3) 7b: 1H NMR (300 MHz, CDCl3) 7.34-7.16 (5 H, m), 5.58 (1 H, d, J 8.3 Hz, NH ), 5.33 (1 H, t, H 3.1 Hz, H(4)), 5.13 (1 H, d d, J 9.5, 3.1 Hz, H(3)), 4.51 (1 H, m, H(2)), 4.25 (1 H, m, H(1)), 4.18-4.06 (3 H, m, H(5), 2xH(6)), 2.75 (1 H, m, CH2CHHPh), 2.61 (1 H, m, CH2CHHPh), 2.13 (3 H, s), 2.08 (3 H, s), 2.05 (3 H, s), 1.98 (1 H, m, CHHCH2Ph), 1.96 (3 H, s), 1.71 (1 H, m, CHHCH2Ph); 13C NMR (75 MHz, CDCl3) 171.4, 171.0, 170.6, 170.4, 141.6, 128.9, 128.7, 126.6, 71.9 (C1), 69.0 (C5), 68.7 (C3), 67.4 (C4), 62.1 (C6), 49.3 (C2), 32.0, 30.1, 23.7, 21.3, 21.2, 21.1; HRMS m/z calcd for C22H29NO8 (M+) 435.1893, found 435.1880. W½ of H(2) signal = 22.5 Hz. 7c: 1H NMR (400 MHz, CDCl3) 7.38-7.15 (5 H, m), 6.08 (1 H, d, J 8.2 Hz, NH), 5.28 (1 H, t, J 3.2 Hz, H(4)), 5.11, (1 H, d d, J 9.3, 3.2 Hz, H(3)), 4.45 (1 H, m, H(2)), 4.31-4.18 (2 H, m, H(1), H(6)), 4.08-3.98 (2 H, m, H(5), H(6)), 3.36-3.19 (2 H, m, CH2CH2SO3Ph), 2.21 (1 H, m, CH2CH2SO3Ph), 2.05 (1 H, m, CH2CH2SO3Ph), 2.05 (3 H, s), 1.99 (3 H, s), 1.95 (3 H, s), 1.93 (3 H, s); 13C NMR (100 MHz, CDCl3) 171.1, 171.0, 170.9, 170.5, 149.4, 130.5, 127.9, 122.4, 70.4 (C1), 69.7 (C5), 68.3 (C3), 67.0 (C4), 61.7 (C6), 49.0 (C2), 47.3, 23.6, 21.6, 21.3 (2 unresolved peaks), 21.1; HRMS m/z calcd for C16H24NO10S (M+-OPh), 422.1119, found 422.1121. W½ of H(2) signal = 24 Hz. 7d: Obtained as a 2:1 mixture of isomers as judged by 1H NMR. This mixture was not resolved using CDCl3 as solvent, and C6D6 was employed. Where it was possible using COSY data, signals corresponding to the same proton are grouped for the two isomers, with the signals assigned to the major component indicated first in the sequence. Where it has not been possible to assign/resolve signals, no such distinction is made. 1H NMR (300 MHz, C6D6) 7.54-7.29 (5 H, m), 6.19/ 6.10 (1 H, d, 7 Hz, NH), 5.89 (1 H, m), 5.64/5.59 (1 H, t, J 3.3 Hz, H(4)), 5.45-5.32 (4 H ,m), 4.99-4.69 (3 H, m), 4.52-4.30 (2 H, m), 3.64/3.60 (3 H, s), 2.34-1.78 (14 H, m, including 8 partially resolved singlets); HRMS m/z calcd for C26H34N2O12 (M+), 566.2112, found 566.2112. In this case, H(2) could not be resolved. 7e: 1H NMR (300 MHz, CDCl3) 5.69 (1 H, d, J 8.3 Hz, NH), 5.33 (1 H, t J 3.3 Hz, H(4)), 5.13 (1 H, d d J 10.0, 3.3 Hz, H(3)), 4.47 (1 H, m, H(2)), 4.30 (1 H, m, H(1)), 4.28- 4.00 (7 H, m , H(5), 2xH(6), 2xOCH2Me), 3.48 (1 H, d d , J 8.0, 6.1 Hz, CH2CH(CO2Et)2), 2.24 (1 H, m, CH2CH(CO2Et)2), 2.12 (3 H, s), 2.06 (6 H, br. s), 2.05 (1 H, m, CH2CH(CO2Et)2), 2.00 (3 H, s), 1.28 (3 H, t, J 7.0 Hz), 1.26 (3 H, t, J 7.0 Hz); 13C NMR (75 MHz, CDCl3) 170.5, 170.1 (broad, 2 signals), 170.0, 169.4, 168.6 (broad, 2 signals), 68.1, 66.7, 61.8, 61.7, 61.0 (2 poorly resolved signals), 48.8, 48.6, 29.7, 23.3, 20.9, 20.7, (2 poorly resolved signals), 14.05, 14.04; HRMS m/z calcd for C22H34NO12 (MH+), 504.2081, found 504.2077. W½ of H(2) signal = 24 Hz. 7f: 1H NMR (300 MHz, CDCl3) 5.73 (1 H, d, J 8.3 Hz, NH), 5.30 (1 H, t, J 3.3. Hz, H(4)), 5.13 (1 H, d d, J 9.8, 3.3 Hz, H(3)), 4.48 (1 H, m, H(2)), 4.23-4.14 (2 H, m, H(1), H(6)), 4.09 (1 H, d d, J 11.5, 5.4 Hz, H(6)), 4.0 (1 H, m, H(5)), 2.38-2.10 (2 H, m, CH2CH2CO2t-Bu), 2.11 (3 H, s), 2.03 (3 H, s), 2.04 (3 H, s), 1.97 (3 H, s), 1.90 (1 H, m, CH2CH2CO2t-Bu), 1.72 (1 H, m, CH2CH2CO2t-Bu), 1.43 (9 H, s); 13C NMR (75 MHz, CDCl3) 172.7, 171.4, 170.9, 170.5 (2 poorly resolved signals), 81.1, 72.1 (C1), 68.9 (C5), 68.6 (C3), 67.3 (C4), 61.8 (C6), 49.2 (C2), 31.7 (CH2CH2CO2t-Bu), 28.5 (t-Bu), 23.7, 21.7 (CH2CH2CO2t-Bu), 21.3, 21.1 (2 poorly resolved signals); HRMS m/z calcd for C17H24NO9 (M+-OtBu), 386.1451, found 386.1459. 7g: 1H NMR (400 MHz, CDCl3) 6.62 (1 H, d, J 8.0 Hz, NH), 5.31 (1 H, t, J 3.3 Hz, H(4)), 5.13 (1 H, d d , J 10.5, 3.3 Hz, H(3)), 4.49 (1 H, m, H(2)), 4.24 (1 H, m, H(1)), 4.10-4.02 (2 H, m, 2xH(6)), 3.96 (1 H, m, H(5)), 3.63 (3 H, s), 2.46-2.27 (2 H, m, CH2CH2CO2Me), 2.09 (3 H, s), 2.00 (6 H, br s), 1.97 (1 H, m, CHHCH2CO2Me), 1.70 (1 H, m, CHHCH2CO2Me); 13C NMR (75 MHz, CDCl3) 173.2, 170.4, 170.0, 72.0 (C1), 68.3 (C5), 67.7 (C3), 66.7 (C4), 61.4 (C6), 51.9 (CO2Me), 49.2 (C2), 29.8 (CH2CH2CO2Me), 26.7, 20.6 (overlapping signals, including CH2CH2CO2Me); HRMS m/z calcd for C18H24F3NO10 (MH+) 472.1431, found 472.1432. W½ of H(2) signal = 24 Hz. 7h: 1H NMR (400 MHz, CDCl3) 7.30-7.05 (5 H, m), 6.51 (1 H, d, J 8.2 Hz, NH), 5.31 (1 H, t, J 3.3 Hz, H(4)), 5.11 (1 H, d d, J 10.5, 3.3 Hz, H(3)), 4.48 (1 H, m, H(2)), 4.23 (1 H, m, H(1)), 4.17-3.96 (3 H, m, H(5) 2xH(6)), 2.65 (1 H, m, CH2CH2Ph), 2.57 (1 H, m, CH2CH2Ph), 2.12 (3 H, s), 2.01 (3 H, s), 1.97 (3 H, s), 1.93 (1 H, m, CH2CH2Ph), and 1.61 (1 H, m, CH2CH2Ph); 13C NMR (100 MHz, CDCl3) 171.0, 170.5, 170.0, 157.0, 140.9, 129.1, 128.7, 126.8, 72.0 (C1), 68.7 (C5), 68.3 (C3), 67.3 (C4), 62.2 (C6), 50.0 (C2), 31.7 (CH2CH2Ph), 30.1 (CH2CH2Ph), 21.1, 21.05, 21.0; HRMS m/z calcd for C22H26F3NO8 (M+) 489.1611, found 489.1616. W½ of H(2) signal = 23 Hz. 7i: 1H NMR (300 MHz, CDCl3) 5.30 (1 H, t, J 3.0 Hz, H(4)), 5.08 (1 H, d d, J 9.0, 3.0 Hz, H(3)), 4.76 (1 H, d, J 8.2 Hz, NH), 4.30-4.12 (4 H, m, H(1), H(2), 2xH(6)), 3.98 (1 H, m, H(5)), 3.67 (3 H, s, CO2Me), 2.33 (2 H, m CH2CO2Me), 2.11 (3 H, s), 2.04 (6 H, br s), 2.02-1.75 (2 H, m CH2CH2CO2Me), 1.42 (9 H, s); 13C NMR (75 MHz, CDCl3) 173.4, 170.6, 170.4, 170.1, 155.2, 80.2, 71.9 (C1), 68.6 (C5), 68.5 (C3), 66.9 (C4), 61.3 (C6), 51.7, 49.5 (C2), 30.0, 28.3, 21.5, 20.8, 20.7 (broad, two signals); HRMS m/z calcd for C21H34NO11 (MH+), 476.2132, found 476.2141. 7j: 1H NMR (300 MHz, CDCl3) 7.28-7.05 (5 H, m), 5.26 (1 H, t, J 2.8 Hz, H(4)), 5.01 (1 H, d d, J 8.7, 2.8 Hz, H(3)), 4.43 (1 H, m, NH), 4.22-3.97 (5 H, m, H(1), H(2), H(5) 2x H(6)), 2.73-2.52 (2 H, m, CH2CH2Ph), 2.06 (3 H, s), 2.10 (3 H, s), 1.97 (3 H, s),1.89 (1 H, m, CHHCH2Ph), 1.76 (1 H, m, CHHCH2Ph)1.34 (9 H, s); 13C NMR (75 MHz, CDCl3) 171.5, 170.6, 170.5, 170.2, 155.1, 141.1, 128.5, 128.4, 126.2, 80.1, 72.2 (C1), 68.7 (C3), 68.6 (C5), 67.3 (C4), 61.7 (C6), 49.5 (C2), 31.5 (CH2CH2Ph), 28.2 (CMe3 and CH2CH2Ph), 21.04, 20.8 (2 overlapping signals), 20.7; HRMS m/z calcd for C21H27NO9 (M+-C4H8), 437.1686, found 437.1682. 3: 1H NMR (400 MHz, CD3OD) 7.25-7.10 (5 H, m), 4.25 (1 H, d d, J 10, 4 Hz, H(2)), 4.05 (1 H, m, H(1)), 3.91 (1 H, t, J 3 Hz, H(4)), 3.80 (1 H, d d, J 10, 4 Hz, H(3)), 3.74-3.62 (3 H, m, H(6), H(5)), 2.77 (1 H, m, CHHCH2Ph), 2.56 (1 H, m, CHHCH2Ph), 1.98 (1 H, m, CH2CHHPh), 1.95 (3 H, m), 1.65 (1 H, m, CH2CHHPh); 13C NMR (75 MHz, CDCl3) 170.9, 140.5, 126.7, 126.5, 123.9, 71.2, 70.1, 62.0, 66.8, 59.5, 49.0, 30.0, 27.4, 19.7; HRMS m/z calcd for C16H24NO5 (MH+) 310.1654, found 310.1653. 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