PDF《Supporting information》

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Z-Formamidoximes in molecular folding and macrocycles'

Weiwen Zhao, Ruiyao Wang, Anne Petitjean* S1 Supporting information Z-Formamidoximes in molecular folding and macrocycles.

Weiwen Zhao, Ruiyao Wang and Anne Petitjean* Table of contents p 1-4 Experimental synthetic details for open structures and macrocycles formamidines. p 5-8 Copy of

1 H,

13 C NMR and selected MS spectra. p

8 Complete stacked plot

1 H NMR ZZ-open, ZZ-M, Tri(ZZ-M) p 9-25 Crystallographic data for ZZ-M (180 K). p 26-40 Crystallographic data for Tri(ZZ-M) (180 K). p 41-46 Crystallographic data for the PyFBn Pyridylamide-Z- formamidoxime diad (180K) [W. Zhao, R. Wang, N. J. Mosey, A. Petitjean, Org. Lett.

2011 in press] N O N H N O PyFBn A. Synthesis Materials and Methods: Commercially available compounds were used as received. Anhydrous dichloromethane and toluene were dried by passing through an activated alumina column. All reactions were performed under Argon (Ar) unless stated otherwise. Deuterated solvents were used as received, except for CDCl3 which was sometimes neutralized by passing through a short column of basic alumina (such treated CDCl3 will be signaled below by an asterisk, i. e. '

CDCl3*'

).

1 H NMR and

13 C NMR were performed using

300 MHz,

400 MHz and

500 MHz Bruker instruments. Peak listings for all NMR spectra are given in ppm and referenced against the solvent residual signal. Thin layer chromatography (TLC) analysis was performed on silica gel with a pore diameter of

60 ? or activated basic Aluminum oxide with a pore diameter of

58 ?. Column chromatography was performed on silica gel with a particle size of 40-63 ?m and a pore diameter of

60 ?. A.1. Retrosynthesis of ZZ-open N O N H H N O Ph O N H H N O Ph ZZ-open N O N H N O N H N O Ph H2N TFA N O NH2 O NH2 DMF-DMA 1Me2 '

Z-Formamidoximes in molecular folding and macrocycles'

Weiwen Zhao, Ruiyao Wang, Anne Petitjean* S2 Bis(N'

,N'

-dimethylformamidyl-N-acyl)-2,6-pyridine (1Me2): Pyridyl-2,6-dicarboxamide (11 mmol, 1.0 eq) was mixed with N,N-dimethylformamide dimethyl- acetal (DMF-DMA,

35 mmol, 3.2 eq) in dimethyl sulfoxide (20 mL). The reaction was heated at

85 °C for 3.5 hours while the methanol by- product distilled off. After cooling to room temperature, the white precipitate was filtered and washed with diethyl ether. The resulting N,N-dimethylformamidine product (74 %) was then used without further purification. δ

1 H NMR (CDCl3*,

500 MHz,

25 °C) 8.59 (s,

2 H), 8.31 (d,

3 J = 7.5 Hz,

2 H), 7.82 (t,

3 J = 7.5 Hz,

1 H), 3.16 (br s,

6 H), 3.11 (br s,

6 H). δ

13 C NMR (CDCl3*,

125 MHz,

25 °C) 176.0, 161.3, 153.5, 137.0, 126.5, 41.3, 35.4. EI+ -HRMS: calc. for C13H17N5O2: 275.1382;

found: 275.1382 [M]+ , 232.0981 [M-Me2N-H]+ , 220.0929 [M-Me2N-H-C]+ , 205.0839 [M-Me2N-H-C-NH]+ . EA calc. for C13H17N5O2: %C 56.71, %H 6.22, %N 25.44;

found %C 56.38, %H 6.20, %N 25.22. Mp

204 °C (dec.). ZZ-open: Bis-reactive formamidine 1Me2 (131 mg, 0.48 mmol, 1.0 eq) was mixed with O- benzylhydroxylamine (117 mg, 0.95 mmol, 2.0 eq) and trifluoroacetic acid (147 ?L, 1.9 mmol, 4.0 eq) in anhydrous dichloromethane (2 mL), and the resulting solution stirred overnight at room temperature. The organic solution was washed with saturated aqueous potassium carbonate (2 mL) and the aqueous layer was extracted with dichloromethane. The combined organic layers were dried over sodium sulphate and concentrated in vacuo. Recrystallization of the crude from 95% ethanol gave a white solid (150 mg,