Supporting Information

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1 Supporting Information Wiley-VCH Weinheim, Germany Selective and Bond Formations through Copper- Catalyzed Aerobic xidative Dehydrogenative Couplings of H-hosphonates Yongbo Zhou, Shuangfeng Yin, Yuxing Gao, Yufen Zhao, Midori Goto, and Li-Biao Han* anie_100344_sm_miscellaneous_information.pdf

2 Table of Contents: I General.....S2 II Synthesis and characterization of complex 3b... S2 III A general procedure for the stoichiometric reaction of H-phosphonates with Cu(Ac) 2 leading to hypophosphates...s4 IV A general procedure for copper-catalyzed aerobic oxidative coupling of H-phosphonates leading to hypophosphates...s5 V A typical procedure for copper-catalyzed aerobic oxidative coupling of H-phosphonates leading to pyrophosphates S6 VI Screening on the catalysts. S7 VII 1 H NMR, 13 C NMR and 31 NMR Spectra......S12 VIII References S17 S-1

3 General. 1 H, 13 C and 31 NMR spectra were recorded on a JEL LA-500 instrument (500 MHz for 1 H, MHz for 13 C, and 1.9 MHz for 31 NMR spectroscopy) or a JEL LA-400 instrument (400 MHz for 1 H, 100 MHz for 13 C, and 162 MHz for 31 NMR spectroscopy). CDCl 3 or benzene-d 6 was used as the solvent. Chemical shift values for 1 H and 13 C were referred to internal Me 4 Si (0 ppm), and that for 31 was referred to H 3 4 (5% solution in D 2, 0 ppm). Elemental analysis was performed by the Analytical Center at the National Institute of Advanced Industrial Science and Technology. Synthesis and characterization of complex 3b H Cu( Ac) 2 THF, rt, N 2 Cu Cu Cu Cu To a capped tube were added the secondary phosphine oxide (h(ch 2 ) 4 ) 2 ()H (6 mmol), anhydrous Cu(Ac) 2 (4 mmol) and THF (10 ml) under nitrogen atmosphere. The reaction mixture was stirred at room temperature for 2 h. Then volatiles were removed under vacuum. The residue was dissolved in THF (5 ml) and Et 2 (5 ml). Hexane (15 ml) was added. The solution was slowly cooled to -30 ºC to give colorless crystals suitable for X-ray analysis. Yield: 1.45 g, 56%. Compound 3b Cu Cu Cu Cu S-2

4 Colorless solid, m.p.: 77 7 ºC. 1 H NMR (benzene-d 6, 400 MHz): δ (m, 32H, CH), (m, H, CH), 2.54 (t, J = 6. Hz, 16H, CH 2 ), 2.32 (s, 12H, CH 3 ) (m, 40H, CH 2 ), (m, H, CH 2 ). 13 C NMR (benzene-d 6, 100 MHz): δ (C), (CH), 12. (CH), 12.7 (CH), (CH), 36.0 (CH 2 ), 33.1 (dd, J C- = 5.7 Hz, J C- = 6.7 Hz, CH 2 ), 32.6 (dd, J C- = 2.5 Hz, CH 2, overlap), 24.5 (CH 3 ), 22.9 (CH 2 ). 31 NMR (benzene-d 6, 162 MHz): δ Anal. Calcd for C H 116 Cu : C, 61.74; H, 6.3. Found: C, 61.36; H, Fig. 1 Molecular structure of complex 3b (H atoms omitted for clarity). S-3

5 Fig. 2 A simplified diagram showing the coordination geometry of complex 3b. A general procedure for the stoichiometric reaction of H-phosphonates with Cu(Ac) 2 leading to hypophosphates. To a capped tube were added H-phosphonate (5 mmol), anhydrous Cu(Ac) 2 (5 mmol) and THF (10 ml) under nitrogen atmosphere. The reaction mixture was stirred at 70 ºC for the time as shown in Table 1. The precipitate was filtered, washed with THF, and then the filtrate was evaporated under vacuum. 25 ml chilled saturated NH 4 Cl solution was added. The product was extracted with CHCl 3, dried over MgS 4, and concentrated under vacuum to give NMR spectroscopically pure coupling products. S-4

6 Table 1. The stoichiometric reaction of H-phosphonates with Cu(Ac) 2. (R) 2 H Cu(Ac) 2 THF, 70 C, 3-5 h (R) 2 (R) 2 1 run H-phosphonate reaciton time (h) product % yield a ( b ) 1 2 (i-r) 2 H (n-bu) 2 H 4 3 (i-r) 2 (n-bu) 2 (i-r) 2 (n-bu) 3 (Et) 2 H 3 (Et) 2 2 (Et) 2 99 (93) 99 (92) 99 (90) 4 (n-c 12 H 25 ) 2 ()H 5 (n-c 12 H 25 ) 2 (n-c 12 H 25 ) 2 9 (91) 5 (hch 2 ) 2 H 4 (hch 2 ) 2 (CH 2 h) 2 99 (94) 6 H 5 9 (90) [a] 31 NMR yields. [b] Isolated yields. A general procedure for copper-catalyzed aerobic oxidative coupling of H- phosphonates leading to hypophosphates. a) To a tube were added Cu(Ac) 2 (3.7 mg, 0.02 mmol) and Et 3 N (0 ul). The mixture was stirred at room temperature for 5 min, then H-phosphonates (1 mmol) was added. The reaction mixture was stirred under dry air atmosphere at room temperature for the time as shown in Table ml chilled saturated NH 4 Cl water solution was added, and the mixture was extracted with CHCl 3, dried over MgS 4, filtered, and concentrated under vacuum to give NMR spectroscopically pure coupling products. b) To a tube were added CuCl (9.9 mg, 0.1 mmol), TEEDA (52.0 mg, 0.30 mmol) and acetone, and the mixture was stirred at room temperature for 5 min. H-phosphonates (1 mmol) was added. The reaction mixture was stirred under dry air atmosphere at room temperature for the time as shown in Table 2. Evaporated the solvent and TEEDA, 10 ml chilled saturated NH 4 Cl water solution was added, and the mixture was extracted with CHCl 3, dried over MgS 4, filtered, and concentrated under vacuum to give NMR spectroscopically pure coupling products. S-5

7 Table 2. Copper-catalyzed aerobic oxidative coupling of H-phosphonates leading to hypophosphates. R 1 R 2 H 2-10 mol% [Cu] Et 3 N or TEEDA, air, rt, R 1 R 2 1 R 1 R 2 run [Cu] (mol%) reaciton time (h) product 2 % yield a ( b ) 1 c Cu(Ac) 2 (2) 4 (i-r) 2 (i-r) 2 9 (93) 2 d CuCl (10) 1.5 (n-bu) 2 (n-bu) 2 94 (0) 3 d CuCl (10) 1.5 (Et) 2 (Et) 2 9 (5) 4 c Cu(Ac) 2 (2) 4 (n-c 12 H 25 ) 2 (n-c 12 H 25 ) 2 95 (4) 5 d CuCl (10) 3 (hch 2 ) 2 (CH 2 h) 2 96 (3) 6 d CuCl (10) 6 96 (4) 7 d CuCl (10) 6 HN N i-r [a] 31 NMR yields. [b] Isolated yields. [c] Cu(Ac) 2 (2 mol%), Et 3N (0.2 ml), (R) 2()H (1 mmol). [d] CuCl (10 mol%), TEEDA (30 mol%), acetone (0.5 ml), and (R) 2()H (1 mmol) (7) Typical procedure for copper-catalyzed aerobic oxidative coupling of H- phosphonates leading to pyrophosphates To a suspension of CuBr 2 (2.2 mg, 0.01 mmol) in 1 ml of acetone, TMEDA (11.6 mg 0.1 mmol) were added. The mixture was stirred at room temperature for 5 min, and then H-phosphonates (1 mmol) was added. The mixture was stirred under dry air for the time as shown in Table 3. Chilled saturated NH 4 Cl water solution was added, and the mixture was extracted with CHCl 3, dried over MgS 4, filtered, and concentrated under vacuum to give NMR spectroscopically pure coupling products. S-6

8 Table 3. Copper-catalyzed aerobic oxidative coupling of H-phosphonates leading to pyrophosphates (R) 2 H 1-2 mol% CuBr 2, mol% TMEDA air, rt R 1 R 2 2 R 1 R 2 run H-phosphonate reaciton time (h) product 2 % yield a ( b ) 1 c 2 c 3 c 4 d (i-r) 2 H (n-bu) 2 H (Et) 2 H (n-c 12 H 25 ) 2 H (hch 2 ) 2 H (i-r) 2 (i-r) 2 (n-bu) 2 (Et) 2 (n-c 12 H 25 ) (99) 100 (99) 100 (99) 99 (9) 5 d 15 (hch 2 ) 2 (CH 2 h) 2 97 (90) 6 d H (96) N 7 d HN i-r H 24 HN N (n-bu) 2 (Et) 2 (n-c 12 H 25 ) 2 i-r 2 9 (91) [a] 31 NMR yields. [b] Isolated yields. [c] CuBr 2 (1 mol%), TMEDA (10 mol%), acetone (1 ml), (R) 2()H (1 mmol). [d] CuBr 2 (2 mol%), TMEDA (15 mol%), THF (1 ml), (R) 2()H (1 mmol). Screening on the catalysts Table 4-1. Copper-catalyzed aerobic oxidative coupling of H-phosphonates with Et 3 N. cat. [Cu]/Et 3 N (i-r) 2 ()H (i-r) 2 (i-r) 2 (i-r) 2 (i-r) 2 air, 25 C 1 mmol 1a 2a Entry Cat. [Cu] (mol%) Et 3 N (ml) Solvent (ml) Time (h) % yield 1a a ( b ) % yield 2a a ( b ) 1 Cu(Ac) 2 (10) 0.2 / (99.2) 0 (0) 2 Cu(Ac) 2 (5) 0.2 / (99.1) 0 (0) 3 Cu(Ac) 2 (2) / acetone (0.5) / / / 4 S (9.7) (0)

9 7 Cu(Ac) 2 (1) 0.2 / 4 CuCl (2) 0.2 / 2 9 CuCl 2 (2) 0.2 / 2 10 CuBr (2) 0.2 / 2 11 CuBr 2 (2) 0.2 / 2 12 CuI (2) 0.2 / 2 13 CuAc (2) 0.2 / 2 14 Cu(N 3 ) 2 3H 2 (2) 0.2 / 2 15 CuS 4 5H 2 (2) 0.2 / 2 16 CuS 4 (2) 0.2 / 2 17 Cu(CCF 3 ) 2 (2) 0.2 / 2 1 Cu(H) 2 (2) 0.2 / 2 19 CuF 2 (2) 0.2 / 2 Cu(acac) 2 (2) 0.2 / 2 21 Cu(acacF 6 ) 2 (2) 0.2 / 2 22 Cu(Tf) 2 (2) 0.2 / 2 23 Cu(Ac) 2 (2) 0.2 / DMF (0.5) DMS (0.5) THF (0.5) CH 3 CN (0.5) Ethanol (0.5) CH 2 Cl 2 (0.5) Toluene (0.5) 2 S

10 CH 3 CC 2 H 5 (0.5) Acetone (0.2) Acetone(0.5) Acetone (1.0) H 2 0 (0.01) H 2 0 (0.02) H 2 0 (0.05) 2 [a] Determined by GC, [b] 31 NMR yields Table CuCl-catalyzed aerobic oxidative coupling of H-phosphonates. (i-r) 2 ()H 1 mmol 5 mol% CuCl/amine (i-r) 2 (i-r) 2 acetone 1 ml, air, 25 C 1a (i-r) 2 2a (i-r) 2 Entry Amine a ( mol%) Time (h) % yield 1a b % yield 2a b H 2 N NH 2 5 Et NH HN Et Et 2 N N Et 2 t-bu NH HN NH t-bu NH 5 7 NH 5 NH 5 9 NH 5 10 MeNH H 2 N 5 12 NH S-9

11 13 Et 3 N N N Me N N [a] Based on N atom. [b] Determined by GC. N Table 4-3. Copper-catalyzed aerobic oxidative coupling of H-phosphonates with TEEDA. cat. [Cu]/TEEDA (i-r) 2 ()H (i-r) 2 (i-r) 2 (i-r) 2 (i-r) 2 air, 25 C 1 mmol 1a 2a Entry Cat. [Cu] (%) TEEDA (mol%) Solvent (ml) Time (h) % yield 1a a ( b ) % yield 2a a ( b ) 1 CuCl (5) 10 acetone (1) Acetone (1) and H 2 (0.02) acetone (1) acetone (1) / CuCl 2 (5) 10 acetone (1) CuBr (5) 10 acetone (1) acetone (1) acetone (1) CuBr 2 (5) 10 acetone (1) CuI (5) 10 acetone (1) Cu(Ac) 2 (5) 10 acetone (1) / CuBr (2.5) / CuBr (10) acetone (1) CuBr (10) / CuBr (10) 30 / (94.7) (5.3) 1 CuCl (10) acetone (1) acetone (1) (97.1) (2.9) / 1.5 h / 1.5 h 96. (97.5) 2.1 (2.0) / 1.5 h Cu(CCF 3 ) 2 (10) / S-10

12 24 Cu(N 3 ) 2 3H 2 (10) / [a] Determined by GC, [b] 31 NMR yields. Table 4-4. Copper-catalyzed aerobic oxidative coupling of H-phosphonates with TMEDA cat. [Cu]/amine (i-r) 2 ()H (i-r) 2 (i-r) 2 (i-r) 2 (i-r) 2 1 mmol air, 25 C 1a 2a Entry cat.[cu] (mol%) amine (mol%) solvent (ml) time (h) % yield 1a a ( b ) % yield 2a a ( b ) 1 CuBr 2 (5) TMEDA (5) acetone (1) TMEDA (10) (0.4) 99.0 (99.3) 3 TMEDA (15) (0.3) 9.0 (99.4) 4 TMEDA (15) acetone (1) and (1.9) 97.3 (97.) H 2 (0.04) 5 TMEDA () acetone (1) (0.3) 9.9 (99.3) 6 CuBr 2 (2.5) TMEDA (2.5) TMEDA (5) TMEDA (7.5) 4 0 (0) 99.1 (100) 9 TMEDA (10) 4 0 (0) 99.1 (100) 10 CuBr 2 (1) TMEDA (5) (2.7) (75.2) 11 TMEDA (7.5) (0.1) (99.9) 12 TMEDA (10) 6 0 (0) (100) TMEDA (10) THF (1) (0) (100) CuBr 2 (0.5) TMEDA (5) acetone (1) CuBr 2 (1) (5) N N 16 CuBr 2 (1) (5) Et NH HN Et 17 CuCl 2 (5) TMEDA (15) CuCl (10) TMEDA (100) neat CuCl (10) TMEDA (0) / CuCl (5) TMEDA (100) / TMEDA (100) acetone (1) TMEDA (0) CuCl (2) TMEDA () TMEDA (50) TMEDA (50) acetone (0.5) TMEDA (100) acetone (1) TMEDA (0) TMEDA (0) Acetone (2) S-11

13 29 CuCl (1) TMEDA (100) acetone (1) TMEDA (0) CuBr (2) TMEDA (100) TMEDA (0) CuBr (1) TMEDA (0) 3 6 [a] Determined by GC, [b] 31 NMR yields H NMR, 13 C NMR and 31 NMR Spectra 1a 1,2 1 H NMR (CDCl 3, 400 MHz): δ (m, 4H, CH), 1.39 (d, 24H, J = 6.4 Hz, CH 3 ). 13 C NMR (CDCl 3, 100 MHz): 72.9 (dd, J C- = 2. Hz, J C- = 3. Hz, CH), 24.3 (dd, J C- = 2.9 Hz, CH 3, overlap), 23. (dd, J C- = 2.9 Hz, J C- = 1.9 Hz, CH 3 ). 31 NMR (CDCl 3, 162 MHz): δ b 1 1 H NMR (CDCl 3, 500 MHz): δ (m, H, CH 2 ), (m, H, CH 2 ), (m, H, CH 2 ), 0.94 (t, 12H, J = 7.3 Hz, CH 3 ). 13 C NMR (CDCl 3, 125 MHz): δ 67.5 (dd, J C- = 2.0 Hz, J C- = 3.1 Hz, CH 2 ), 32.4 (dd, J C- = 3.1 Hz, CH 2, overlap), 1.6 (CH 2 ), 13.5 (CH 3 ). 31 NMR (CDCl 3, 2 MHz): δ 6.6. S-12

14 1c 3,4 1 H NMR (CDCl 3, 500 MHz): δ (m, H, CH 2 ), 1.3 (t, 12H, J = 7.0 Hz, CH 3 ). 13 C NMR (CDCl 3, 125 MHz): δ 63.9 (dd, J C- = 3.1 Hz, CH 2, overlap), 16.4 (dd, J C- = 3.1 Hz, CH 3, overlap). 31 NMR (CDCl 3, 2 MHz): δ d Wax solid. m.p.: ºC. 1 H NMR (CDCl 3, 400 MHz): δ (m, H, CH 2 ), (m, H, CH 2 ), (m, 0H, CH 2 ), 0. (t, 12H, J = 6. Hz, CH 3 ). 13 C NMR (CDCl 3, 100 MHz): δ 67. (dd, J C- = 3. Hz, CH 2, overlap), 31.9 (CH 2 ), 30.5 (dd, J C- = 2.9 Hz, CH 2, overlap), 29.7 (CH 2 ), 29.7 (CH 2 ), 29.6 (CH 2 ), 29.6 (CH 2 ), 29.4 (CH 2 ), 29.2 (CH 2 ), 25.4 (CH 2 ), 22.7 (CH 2 ), 14.1 (CH 3 ). 31 NMR (CDCl 3, 162 MHz): δ 6.6. Anal. Calcd for C 4 H : C, 69.02; H, Found: C, 6.72; H, e 5 1 H NMR (CDCl 3, 400 MHz): δ (m, H, CH), (m, H, CH 2 ). 13 C NMR (CDCl 3, 100 MHz): δ (dd, J C- = 2. Hz, J C- = 3. Hz, CH), 12.7(CH), 12.6(CH), 12.2(CH), 69.2 (dd, J C- = 2.9 Hz, CH 2, overlap). 31 NMR (CDCl 3, 162 MHz): δ S-13

15 1f 6 1 H NMR (CDCl 3, 400 MHz): δ 4.67 (d, 4H, J = 10.4 Hz, CH 2 ), (m, 4H, CH 2 ), 1.35 (s, 6H, CH 3 ), 0.9 (s, 6H, CH 3 ). 13 C NMR (CDCl 3, 100 MHz): δ 7. (dd, J C- = 3. Hz, CH 2, overlap), 32.7 (dd, J C- = 3. Hz, J C- = 4. Hz, (CH 2 ) 2 C(CH 3 ) 2 ), 22.0 (CH 3 ),.2 (CH 3 ). 31 NMR (CDCl 3, 162 MHz): δ g N HN i-r i-r N NH White solid. m.p.: ºC. 1 H NMR (CDCl 3, 400 MHz): δ 9.30, 9.25 and 9.23 (3s, 2H, NH), 7.2, 7.25 and 7.22 (3d, 2H, J = 1.2 Hz, H6-thymine), 7.01 (s, broad, 2H, H1'), (m, 2H, H3'), (m, 2H, H2'), 5.00 (s, broad, 2H, H4'), (m, 2H, CH-isopropyl), (m, 4H, H5'), 1.92, 1.92 and 1.91 (3s, broad, 6H, CH 3 -thymine), (m, 12H, CH 3 -isopropyl). 13 C NMR (CDCl 3, 100 MHz): δ and 163. (2s, broad, C4-thymine), and 150. (2s, broad, C2- thymine), (d, J C- = 2.9 Hz, C6-thymine), and (2s, broad, C6-thymine), 132. and 132. (2s, broad, C3'), (d, J C- = 2. Hz, C3', ), (dd, J C- = 3. Hz, C2', overlap), (s, broad, C2') and (2s, broad, C5-thymine), 9.7 and 9.6 (2s, broad, C1'), 4.5, 4.4 and 4.3 (3d, J C- = 3. Hz, C4'), 74.5, 74.5 and 74.3 (3s, broad, CH-isopropyl), 6.0, 67. and 67.7 (3s, broad, C5'), 24.3 and 23. (2s, broad, CH-isopropyl), 12.4 (s, broad, CH 3 -thymine). 31 NMR (CDCl 3, 162 MHz): δ 6.33 and 5.91 (broad). Anal. Calcd for C 26 H 36 N : C, 47.42; H, 5.51; N,.51. Found: C, 47.71; H, 5.35; N,.2. 2a 7, S-14

16 1 H NMR (CDCl 3, 400 MHz): δ (m, 4H, CH), 1.3 (d, 24H, J = 6.0 Hz CH 3 ). 13 C NMR (CDCl 3, 125 MHz): δ 74.1 (dd, J C- = 3.1 Hz, CH, overlap), 23.6 (dd, J C- = 3.1 Hz, CH 3, overlap), 23.5 (dd, J C- = 3.1 Hz, CH 3, overlap). 31 NMR (CDCl 3, 2 MHz): δ b 9,10 1 H NMR (CDCl 3, 500 MHz): δ (m, H, CH 2 ), (m, H, CH 2 ), (m, H, CH 2 ), 0.94 (t, 12H, J = 7.3 Hz, CH 3 ). 31 NMR (CDCl 3, 2 MHz): δ , 11 2c 1 H NMR (CDCl 3, 400 MHz): δ (m, H, CH 2 ), 1.34 (t, 12H, J = 7.0 Hz, CH 3 ). 13 C NMR (CDCl 3, 100 MHz): δ 65.1 (dd, J C- = 2. Hz, CH 2, overlap), 15.9 (dd, J C- = 2. Hz CH 3, J C- = 3. Hz). 31 NMR (CDCl 3, 162 MHz): δ d Wax solid. m.p.: ºC. 1 H NMR (CDCl 3, 400 MHz): δ (m, H, CH 2 ), (m, H, CH 2 ), (m, 0H, CH 2 ), 0.9 (t, 12H, J C- = 6. Hz, CH 3 ). 13 C NMR (CDCl 3, 100 MHz): δ 69.2 (dd, J C- = 2.9 Hz, CH 2, overlap), 32.0 (CH 2 ), 30.2 (dd, J C- = 2. Hz, J C- = 3. Hz, CH 2 ), 29. (CH 2 ), 29.7 (CH 2 ), 29.7 (CH 2 ), 29.6 (CH 2 ), 29.4 (CH 2 ), 29.2 (CH 2 ), 25.4 (CH 2 ), 22.7 (CH 2 ), 14.2 (CH 3 ). 31 NMR (CDCl 3, 162 MHz): δ Anal. Calcd for C 4 H : C, 67.73; H, Found: C, 6.01; H, S-15

17 2e 1 H NMR (CDCl 3, 400 MHz): δ (m, H, CH), (m, H, CH 2 ). 13 C NMR (CDCl 3, 100 MHz): δ (dd, J C- = 3. Hz, CH, overlap), 12.7 (CH), 12.5 (CH), 12.0 (CH), 70.4 (dd, J C- = 2.9 Hz, CH 2, overlap). 31 NMR (CDCl 3, 162 MHz): δ f 12,13 1 H NMR (CDCl 3, 400 MHz): δ 4.4 (d, 4H, J = 10. Hz, CH 2 ), (m, 4H, CH 2 ), 1.32 (s, 6H, CH 3 ), 0.90 (s, 6H, CH 3 ). 13 C NMR (CDCl 3, 100 MHz): δ 79.0 (dd, J C- = 3. Hz, CH 2, overlap), 32.2 (dd, J C- = 2.9 Hz, J C- = 3. Hz, (CH 2 ) 2 C(CH 3 ) 2 ), 21.9 (CH 3 ), 19.9 (CH 3 ). 31 NMR (CDCl 3, 162 MHz): δ g HN N i-r i-r N NH White solid. m.p.: ºC. 1 H NMR (CDCl 3, 400 MHz): δ 9.50, 9.47 and 9.44 (3s, 2H, NH), 7.29, 7.2 and 7.22 (3s, broad, H6-thymine), 7.02, 7.01 and 7.00 (3s, broad, 2H, H1'), (m, 2H, H3'), 5.90 (s, broad, 2H, H2'), 4.99 (s, broad, 2H, H4'), (m, 2H, CH-isopropyl), (m, 4H, H5'), 1.91, and 1.91 (2s, broad, 6H, CH 3 -thymine), (m, 12H, CH 3 -isopropyl). 13 C NMR (CDCl 3, 100 MHz): δ and (2s, broad, C4-thymine), and (2s, broad, C2- thymine), 135. and (2s, broad, C6-thymine), 132. and (2s, broad, C3'), (d, J C- = 4. Hz, C3'), 127., 12.7 and (3s, broad, C2'), 111.4, 11.4 and (3s, broad, C5-thymine), 9.6 and 9.5 (2s, broad, C1'), 4.3, 4.2 and 4.1 (3s, broad, C4'), 75.7 (s, broad, CH-isopropyl), 75.6 (d, J C- = 4. Hz, CH-isopropyl), 75.5 (s, broad, CH-isopropyl), 6.6, 67.5 and 6.5 (3s, broad, C5'), 23.6 and 23.4 (2s, broad, CH-isopropyl), 12.4 and 12.3 (2s, broad, CH 3 -thymine). 31 NMR (CDCl 3, 162 S-16

18 MHz): δ (broad) and Anal. Calcd for C 26 H 36 N : C, 46.30; H, 5.3; N,.31. Found: C, 46.01; H, 5.15; N,.54. References: 1. Michalski, J.; Zwierzak, A. Bull. Acad. olon. Sci., Ser. Sci. Chim. 1965, 13, Romakhin, A. S.; Zagumennov, V. A.; Nikitin, E. V. J. Gen. Chem. USSR (Engl. Transl.) 1997, 67, Ruflin, C.; Fischbach, U.; Grutzmacher, H.; Levalois-Grutzmacher, J. Heteroatom Chem. 07, 1, Kers, A.; Stawinski, J.; Dembkowski, L.; Kraszewski, A. Tetrahedron 1997, 53, Rosenheim; insker Chem. Ber. 1910, 43, Nycz, J. E.; Musiol, R. Heteroatom Chem. 06, 17, Hutchinson, D. W.; Thornton, D. M. J. rganomet. Chem. 19, 340, 93.. Jaszay, Z. M.; etnehazy, I.; Toke, L. Heteroatom Chem. 04, 15, udovik, A. N.; Kovtun, V. Y.; Khairullin, V. K.; Vasyanina, M. A. J. Gen. Chem.USSR (Engl. Transl.) 1992, 62, Toy, A. D. F. J. Am. Chem. Soc. 194, 70, Kinas, R. W.; kruszek, A.; Stec, W. J. Tetrahedron Lett. 02, 43, Cullis,. M.; Kay,. B.; Trippett, S. J. Chem. Soc. Chem. Comm. 195, Nycz, J. E. oll. J. Chem. 09, 3, 59. S-17

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