Clinical characteristics of urosepsis caused by extended-spectrum beta-lactamase-producing Escherichia coli or Klebsiella pneumonia and their emergence in the community

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Synthesis of long-chained oligo-a-aminopyridines by tandem

Pd-catalyzed cross-coupling aminations and their helical

dinuclear complexes

Hasan Hasanov,

a,b,

Uan-Kang Tan,

b,c,

Rui-Ren Wang,

a

Gene Hsiang Lee

a

and

Shie-Ming Peng

a,b,*

a_{Department of Chemistry, National Taiwan University, Taipei, Taiwan} b

Institute of Chemistry, Academia Sinica, Taipei, Taiwan

c_{Department of Chemical Engineering, Kuang Wu Institute of Technology, Taipei, Taiwan}

Received 25 June 2004; revised 28 July 2004; accepted 6 August 2004

Abstract—Three novel multidentate long-chained oligo-a-aminopyridine ligands, nonapyridyloctaamine (1, npoa), decapyridylnona-amine (2, dpna), and undecapyridyldecadecapyridylnona-amine (3, upda) were synthesized successfully by tandem Pd-catalyzed cross-coupling ami-nations. The helical structures of protonated ligand npoa {4, [H4Ænpoa](SO3CF3)4} and the related dinuclear complexes 5–10 were synthesized and characterized by X-ray diﬀractions.

Aminopyridines are frequently used as building blocks for synthetic transformations.1–3 _{On the basis of their}

polynucleating abilities, their derivatives are often stud-ied in organometallic chemistry,4 _{and have industrial}

applications such as ﬂuorescent dyes.5,6

Oligo-a-amino-pyridines provide multidentate sites with signiﬁcant ﬂexi-bility that can produce the helical structures either by intramolecular hydrogen bond formation or self-assem-bly with metal ions into distinct binding sites. A series of a-aminopyridine ligands and various helicates have been reported, such as tetrapyridyltriamine,2

pentapyridyl-tetraamine,2 _{hexapyridylpentaamine,}7a

heptapyridyl-hexaamine,7b _{and octapyridylheptaamine}7c _{from our}

laboratory, and dinuclear triple helicates from Albr-echts bis-catecholate ligands8 _{and Piguets}

bis-terden-tate ligands;9 _{dinuclear double helicates from Rices}

pyridylthiazole ligands10_{and Constables quaterpyridine}

ligands.11 _{A key to success in assembling these helical}

aminopyridines is the eﬃcient reaction process from the halopyridines as the starting materials. The prepara-tion of aminopyridines in most studies utilized aromatic nucleophilic substitution SNAr, benzyne or SRN1

reac-tions.12,13 _{These methods are diﬃcult to apply in the}

consecutive synthesis of polyaminopyridines due to the poor yields, low selectivity from the nucleophilic regio-control, the high reaction temperature, and the presence of speciﬁc functionality on the heterocyclic rings.12

Buch-wald and others have recently developed cross-coupling amination to generate mono-aminopyridines starting from their corresponding halopyridines catalyzing with Pd(0)/bis-phosphine complexes.12,14,15 _{The advantages}

of Pd-catalyzed C–N aminations are mild reaction con-ditions with high yields; hence this method is utilized to synthesize helical long-chained oligo-a-aminopyridines 1–3 eﬀectively.

Oligo-a-aminopyridines provide multibinding capabili-ties with the metal centers, either (i) through nitrogen atoms from both pyridines and amines,16 _{or (ii) only}

pyridines,17 _{or (iii) only amines, with three diﬀerent}

binding modes, syn–syn, anti–anti, and syn–anti (Fig. 1).18 _{These metal complexes are very interesting for}

Keywords: Helical; Dinuclear metal complexes; Oligo-a-amino-pyridines.

* Corresponding author. Tel.: +886 2 23638305; fax: +886 2 23636359; e-mail:smpeng@ntu.edu.tw

These authors contributed equally.

N N N N N N N N N (a) (b) (c)

Figure 1. Types of (a) syn–syn, (b) anti–anti, (c) syn–anti. Tetrahedron Letters 45 (2004) 7765–7769

Tetrahedron

Letters

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fundamental studies of special physical properties, coor-dination,19 _{metal–metal interactions,}20–25 _{the assembly}

of helicates,9 _{and biological enzymatic}

transforma-tions.26–32 _{For example, dinickel and dicopper}

com-plexes promote urease30 _{and oxygenase reactions,}

respectively.31 _{Furthermore, the syn–syn conformation}

was ﬁrst found in linear Cu3(dpa)4Cl2,33 _anti–anti

con-formation was observed in Cu(bipyam)234 _and

Cu-(mpa)2,17_{and anti–syn conformation was only observed}

in the dimers of free ligands.33 _{In short, the geometries}

of the metal helicates are mainly controlled by the par-tition of binding sites from the ligands while linked to distinct metal centers. It is interesting to assemble long-chained oligo-a-aminopyridines, such as nonapyr-idyloctaamine (1, npoa), decapyridylnonaamine (2, dpna), and undecapyridyldecaamine (3, upda) by employing Buchwalds tandem cross-coupling amina-tion with catalyzaamina-tion by the Pd(0) complex/BINAP or DPPP, and their helical dinuclear metal complexes 5– 10. The complexes possess unique features, and have the general formula [M2(L)(ClO4)m(S)n](ClO4)oÆ(sol-vent)p where M = Ni or Cu, S = solvent, m = 0–1, n = 0–3, o = 3–4, p = 0–5.

The synthesis of novel long-chained oligo-a-aminopyr-idines 1–3 are shown in Scheme 1 where pyridine was employed as the media to replace the commonly used solvents due to its high solvating ability for the desired adducts, and successful catalyzation of the cross-cou-pling reaction.18

Ligand 1 was obtained via double Pd-catalyzed cross-coupling aminations from (A) and (B), and then subse-quent reaction with a half equivalent of 2,6-diaminopyr-idine.35_{A ﬁnal yield of 63% was achieved. Ligand 2, in a}

similar manner, was produced from (A) with an overall 41% yield via four sequential Pd-catalyzed aminations.36

Ligand 3 was prepared through a Pd-catalyzed amina-tion from bromo-substrate (E) and amino-substrate (F) in 33% yield.37 _{The crystal structure 4,}38

[H4Ænpoa]-(SO3CF3)4, a protonated form of ligand 1, is shown in

Figure 2. It has a highly helical conformation due to its unique intramolecular hydrogen bonds (N1– H N3, N5–H N7, N11–H N9, N11–H N13, and N17–H N15). The TGA data of ligands 1–3 show high thermal stability (500 °C), which is consistent with Jorgensons theory.3

The dinuclear metal complexes 5–10 (Fig. 4) were pre-pared by mixing 1 equiv of Ni(ClO4)2or Cu(ClO4)2with 0.55 equiv of synthetic ligands 1–3, respectively, and then growing crystals in the appropriate solvent systems by diﬀusion techniques. The geometry for both nickel centers demonstrate slightly distorted octahedral in the light blue compound 5 {[(Ni2npoa)(CH3CN)2(H2O)]-[ClO4]3Æ(OH)Æ(H2O)Æ(CH3CN)4} (Fig. 4),39 _N(11)–N–

(12)–N(13) has a syn–syn conformation, and this molecule has a bent-helical structure (Fig. 3) with approximately 1.5 helical turns, and the full length is around 4.2 nm. The molecular structure of the deep green compound 6 {[(Cu2npoa)][ClO4]4Æ(CH3CN)3Æ (H2O)1.5}, with a distorted square planar geometry for Cu(1), and a distorted square pyramidal geometry for Cu(2),40_{and a regular-helical structure (}_{Fig. 3}_{) with a}

syn–anti arrangement of N(9)–N(10)–N(11). This mole-cule shows more than two helical turns, and its full length is approximately 4.3 nm. Diﬀerent coordination geometries for two nickel centers are observed in the yellowish-green compound 7 {[(Ni2dpna)(ClO4)][ClO4]3Æ (CH3NO2)Æ(CH3CN)Æ(C2H5OC2H5)2Æ(CH3OH)} where Ni(1) exhibits a distorted square pyramid geometry and Ni(2) has an octahedral shape.41_{The conformation}

of N(7)–N(8)–N(9) has a syn–syn arrangement, and the whole molecule has a bent-helical structure with approximately two turns, and a length of around 4.8 nm. In the structure of the deep green compound 8 {[(Cu2dpna)][ClO4]4Æ(CH3OH)2} where both copper ions have distorted square pyramid geometries,42_the

confor-mation of N(9)–N(10)–N(11) has a syn–syn geometry, and the whole molecule also has a bent-helical structure with approximately two turns, its full length is around

N N H H2N N Br Pd2(dba)3, BINAP, N N H N N H N NH N Br H2N N Br t-BuONa, THF Pd(PPh3)4, DPPP N N N N H N H NH2 (F) N NH2 H2N

Pd2(dba)3, BINAP, t-BuNa,, Benzene

(D) (C) t-BuONa, Pyridine Pd(PPh3)4, DPPP (E) N N H N NH N N H N Br N H N N N N N H NH dpna (2) (A) t-BuNa, Benzene 4 8 80% 85% 80% 75% N N N N H NH upda (3) 9 t-BuONa, Pyridine Pd(PPh3)4, DPPP 60% (E) N N H H2N N Br N N N Br H (B) Pd2(dba)3, BINAP t-BuONa, Benzene (A) t-BuONa, THF Pd(PPh3)4, DPPP N N N N H N H (C) npoa (1) N N H N N H N N H N Br N NH2 H2N 7 1/2 90% 70% Scheme 1.

Figure 2. The ORTEP structure of the cationic part in compound 4, thermal ellipsoids 30% probability level.

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4.6 nm. The geometry for the nickel ions in the yellow-ish-orange compound 9, {[(Ni2upda)][ClO 4]4Æ(CH3-NO2)Æ(CH3OH)3.5} where Ni(1) has a distorted square pyramid geometry and Ni (2) exhibits an octahedral shape;43 _{N(11)–N(12)–N(13) has a syn–syn}

conforma-tion, and the whole molecule has a bent-helical struc-ture with more than two turns, its rough length is around 5.2 nm. Both copper ions have distorted square planer shapes (Fig. 4)44 _{in the deep green compound}

10 {[(Cu2upda)][ClO4]4Æ(CH2Cl2)0.5Æ(CH3NO2)4Æ(H2O)3}, and all the nitrogen linkage arrangements have anti–anti conformations, the whole molecule has a regular-heli-cal structure with more than three complete turns, and its rough length is around 5.8 nm.

The magnetic properties were measured using ground powders of the dinuclear compounds 5–1035–40 _(at

10 kG), and a simple spin-only model of magnetic moment (leﬀ)45 _{was adapted due to their long metal–}

metal distances. The leﬀ= [n1(n1+ 2) + n2(n2+ 2)] 1/2

, where n1 represents the unpaired electrons of metal (1), and n2 represents the unpaired electrons of metal (2), was calculated. Dinickel compounds 5, 7, and 9 have leﬀ= 3.9, 4.0, and 4.2, respectively, that are close to the high spin predicted value, leﬀ= [2(2 + 2) + 2(2 + 2)]1/2= 4.0. The dicopper compounds 6, 8, and 10 all

have leff= 2.3, which agrees with the predicted value leff= [1(1 + 2) + 1(1 + 2)]1/2= 2.4. The magnetic studies have revealed that the dinickel complexes (5, 7, and 9) exhibit a slight antiferromagnetic behavior at tempera-ture < 50 K, and paramagnetic properties at all other tested temperatures. The dicopper complexes (6, 8, and 10) show paramagnetic behaviors at all recorded tem-peratures. This indicates that these magnetic behaviors for the dinuclear complexes are actually similar to their corresponding mononuclear complexes. The paramag-netic behaviors are also consistent with the NMR obser-vations where the downfield peaks occur at 10–20 ppm for metal complexes versus their corresponding free ligands.

This work reports the eﬀective synthesis of novel helical oligo-a-aminopyridine ligands 1–3 by tandem Pd-cata-lyzed cross-coupling amination, and their correspond-ing dinuclear (Ni2+/Ni2+ and Cu2+/Cu2+) metal complexes 5–10. Ligands 1–3 show coordination to the metal centers only through the nitrogen atoms on the pyridine rings. Only dinuclear complexes 6 and 10 show regular-helical structures and with weak p–p interac-tions. It is worthwhile to note that the dinuclear com-plexes 5–10 exhibit the longest metal–metal distances that have been reported for complexes with oligo-a-ami-nopyridine ligands, with distances between the metal centers of 6.042, 4.639, 6.231, 5.836, 5.900, and 7.420 A˚, respectively.

Crystallographic data for the structural analysis have been registered in the Cambridge Crystallographic Data Center: compound 4 was registered as CCDC No. 201554, compound 5 as CCDC No. 201556, compound 6 as CCDC No. 201555, compound 7 as CCDC No. 201558, compound 8 as CCDC No. 201557, compound 9 as CCDC No. 201560, and compound 10 as CCDC No. 201559. Information may be obtained free of charge from the Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax: +44-1223-336033; e-mail: depos-it@ccdc.cam.ac.uk orhttp://www.ccdc.cam.ac.uk).

Acknowledgements

We thank the National Science Council and the Minis-try of Education of the Republic of China for the ﬁnan-cial supports.

References and notes

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35. npoa, nonapyridyloctaamine, 1: Anal. Calcd for C45H37N17: C 66.25, H 4.57, N 29.18. Found: C 66.36, H 4.56, N 29.08. IR (KBr): 3408, 3310, 3205, 3021, 1674, 1582, 1431, 1307, 1149, 1774, 1149, 715 cm1. 1H NMR (400 MHz, DMSO-d6): d 9.38 (s, 2H, NH), 9.09 (s, 6H, NH), 6.83–8.21 (m, 29H, aromatic H). FAB/MS [m/z]: [816 (M)+].

36. dpna, decapyridylnonaamine, 2: Anal. Calcd for C50H41N19: C 66.14, H 4.55, N 29.31. Found: C 66.43, H 4.42, N 29.15. IR (KBr): 3448, 3310, 3198, 1635, 1562, 1516, 1418, 1352, 1155 cm1.1H NMR (400 MHz, DMSO-d6): d 8.49 (s, 2H, NH), 8.20 (s, 7H, NH), 5.99–7.35 (m, 32H, aromatic H). FAB/MS [m/z]: [908 (M)+_].

37. upda, undecapyridyldecaamine, 3: Anal. Calcd for C55H45N21: C 66.05, H 4.54, N 29.41. Found: C 66.30, H 4.38, N 29.32. IR (KBr): 3416, 3204, 2952, 1587, 1514, 1434, 1308, 778 cm1.1_{H NMR (400 MHz, DMSO-d} 6): d 9.36 (s, 2H, NH), 9.06 (s, 8H, NH), 6.84–8.20 (m, 35H, aromatic H). FAB/MS [m/z]: [1000 (M)+].

38. Crystallographic data for 4: C52H45.50F12N18.50O12S4, M = 1477.81, monoclinic, space group C2/c, a = 26.5696 (11), b = 14.6662 (6), c = 33.9125 (14), a = 90°, b = 111.3060° (10), c= 90°, V = 12311.7 (9) A˚3, Z = 8, Dcalcd= 1.595 g/cm3, l(MoKa) = 0.268 mm1, k = 0.71073A˚ , T = 150 (1) K, h= 1.29–26.43°, Tmin/Tmax= 0.8562/ 0.9280, independent reﬂns. = 12606 (Rint= 0.0850), Rf= 0.0549, GOF = 1.059. The structure was solved in Bruker SMART by direct method and expanded by using Fourier techniques, the functions were minimized during least-squares cycles where R = RjjF0jjFcjj/RjF0j; ðF2

0Þ ¼ ½RfwðF20 F2cÞ

2_g=RfwðF2 0Þ

2_g1=2_{. The} nonhydro-gen atoms were reﬁned anisotropically.

39. Crystallographic data for 5: C57H60Cl3N23Ni2O15, M = 1531.05, triclinic, space group P1, a = 11.8920 (6), b = 13.8128 (7), c = 22.5784(12), a = 83.140° (1), b = 83.697° (1), c = 86.049° (1), V = 1852.83 (3) A˚3, Z = 2, Dcalcd= 1.392 g/cm3, l(MoKa) = 0.701 mm1, k= 0.71073 A˚ , T = 150 (1) K, h= 0.91–26.37°, Tmin/Tmax= 0.6904/ 0.8621, independent reﬂns. = 14936 (Rint= 0.0881). Rf= 0.0896, GOF = 1.024. The structure was solved in Bruker SMART with the same method described previously. 40. Crystallographic data for 6: C51H49Cl4N20Cu2O17.50,

M = 1490.98, monoclinic, space group P21/c, a = 22.3833 (12), b = 13.1494 (7), c = 20.6251 (11), a = 90°, b = 101.995° (1), c = 90°, V = 5938.0 (5) A˚3

, Z = 4 , Dcalcd= 1.668 g/cm3, l(MoKa) = 0.987 mm1, k= 0.71073 A˚ , T = 150 (1) K, h = 2.43–27.50°, Tmin/Tmax= 0.7154/ 0.8311, independent reﬂns. = 13624(Rint= 0.0331). Rf= 0.0451, GOF = 1.014. The structure was solved in

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Bruker SMART with the same method described previously.

41. Crystallographic data for 7: C62H71Cl4N21Ni2O21, M = 1705.62, triclinic, space group P1, a = 14.6520 (1), b = 15.4574 (1), c = 17.5339 (2), a = 100.7550° (4), b = 98.3837° (4), c = 110.4784° (4), V = 3557.37 (5) AA3, Z = 2, Dcalcd= 1.592 g/cm3, l (MoKa) = 0.770 mm1, k = 0.71073 A˚ , T = 150 (1) K, h = 2.43–27.50°, Tmin/Tmax= 0.774/0.942, independent reﬂns. = 16291 (Rint= 0.0662). Rf= 0.0665, GOF = 1.021. The structure was solved in Nonius KappaCCD with the same method described previously.

42. Crystallographic data for 8: C52H49Cl4N19Cu2O18, M = 1496.98, monoclinic, space group P21/c, a = 15.4476 (3), b = 14.4702 (2), c = 25.9158 (6), a = 90°, b = 98.3837° (4), c = 90°, V = 5735.39 (19) A˚3_{, Z = 4 , D}

calcd= 1.734g/ cm3_{, l(MoK}

a) = 1.022 mm1, k = 0.71073 A˚ , T = 150 (1) K, h = 1.92–25°, Tmin/Tmax= 0.5449/0.8950, independent reﬂns. = 10088 (Rint= 0.0768). Rf= 0.0546, GOF = 1.051. The structure was solved in Nonius KappaCCD with the same method described previously.

43. Crystallographic data for 9: C59.50H62Cl4N22Ni2O21.50, M = 1688.53, monoclinic, space group P21/n, a = 11.0634 (1), b = 24.8780 (2), c = 25.0143 (2), a = 90°, b = 101.0158° (3), c = 90°, V = 6757.96 (10) A˚3, Z = 4 , Dcalcd= 1.660 g/ cm3, l(MoKa) = 0.811 mm1, k = 0.71073 A˚ , T = 150 (1) K, h = 1.8427.50°, Tmin/Tmax= 0.646/0.931, independent reﬂns. = 15455 (Rint= 0.0581). Rf= 0.0826, GOF = 1.040. The structure was solved in Nonius KappaCCD with the same method described previously.

44. Crystallographic data for 10: C59.50H64Cl5N25Cu2O27, M = 1865.69, monoclinic, space group P21/n, a = 11.6942 (2), b = 26.4115 (5), c = 25.0251 (5), a = 90° (1), b = 99.730° (1), c = 90°, V = 7618.1 (2) A˚3

, Z = 4 , Dcalcd= 1.627 g/cm3, l(MoKa) = 0.832 mm1, k = 0.71073 A˚ , T = 150 (1) K, h = 2.07–25°, Tmin/Tmax= 0.830/0.974, inde-pendent reﬂns. = 13385 (Rint= 0.0747). Rf= 0.1624, GOF = 1.058. The structure was solved in Non-ius KappaCCD with the same method described previously.

45. Teweldemedhin, Z. S.; Fuller, R. L.; Greenblatt, M. J. Chem. Edu. 1996, 73, 906–909.