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United States Patent (19) 11 Patent Number: 6,051,704 Gordon-Wylie Et Al

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United States Patent (19) 11 Patent Number: 6,051,704 Gordon-Wylie Et Al US006051704A United States Patent (19) 11 Patent Number: 6,051,704 Gordon-Wylie et al. (45) Date of Patent: Apr. 18, 2000 54 SYNTHESIS OF MACROCYCLIC Erich Stuart Uffelman, Macrocyclic Tetraamido-N Ligands TETRAAMIDO-N LIGANDS that Stabilize High Valent Complexes of Chromium, Maganese, Iron, Cobalt, Nickel and Copper, California 75 Inventors: Scott W. Gordon-Wylie; Terrence J. Institute of Technology, Aug. 19, 1991. Collins, both of Pittsburgh, Pa. Theodora W. Greene, Protective Groups in Organic Synthe sis, Harvard University, John Wiley & Sons, 1981. 73 Assignee: Carnegie Mellon University, Kimberely K. Kostka, Synthesis and Characterization of Pittsburgh, Pa. High-Valent Iron Complexes of Macrocyclic Tetraamido-N Ligands, Carnegie Mellon University, Jul. 19, 1993. 21 Appl. No.: 08/681,187 Nathan L. Drake, Harry D. Anspon, et al. Synthetic Anti marlarials. Some Derivatives of 8-Aminoquinoline, Labo 22 Filed: Jul. 22, 1996 ratories of the University of Maryland, vol. 68, p. 1536, Aug. 51) Int. Cl." ....................... C07D 403/02; CO7D 259/00 1946. 52 U.S. Cl. .......................... 540/465; 540/451; 540/460; Richard J. Bushby and Michael D. Pollard, The Introduction of Alkylidene Substituents into the 4-Position of the 3,3,5, 540/463; 540/450 5, Tetramethyl-A-pyrazoline Nucleus by the Thioketone 58 Field of Search ..................................... 540/450, 451, plus Diazoalkane Reaction: Synthesis of Tetrasubstituted 540/460, 452, 453, 465, 463 Episulphides and Alkenes. 56) References Cited Primary Examiner Mukund J. Shah Assistant Examiner Pavanaram K. Sripada U.S. PATENT DOCUMENTS Attorney, Agent, or Firm Kirkpatrick & Lockhart LLP 4,517,122 5/1985 Tomalia et al. ...................... 260/239.3 57 ABSTRACT 4,577,042 3/1986 Collins et al. ... ... 564/158 4,758,682 7/1988 Collins et al. ............................ 534/14 New Synthetic methods for the preparation of macrocyclic 5,189,160 2/1993 Memeger, Jr. ... ... 540/460 amido-N donor ligands are provided. The primary method of 5,247,075 9/1993 Parker et al. ... ... 540/465 the present invention involves in general only two Synthetic 5,298,618 3/1994 Speranza et al. ....................... 540/460 Steps. In the first Step, an C. or 3 amino carboxylic acid is OTHER PUBLICATIONS allowed to react with an optimal (approximately Stoichiometric) amount of an activated malonate or oxalate Bradshaw et al. Chap IV in Aza-Crown Macrocycles, Inter derivative with mild heating. Upon completion of the double science Publication, Joh Wiley 1993 p. 146. coupling reaction, hydrolysis of the reaction mixture yields A. Paul Krapcho, Edwin G. E. Jahngen, Jr., and David S. a diamide containing intermediate (a macro linker). In the Kashdan, Route to Monoesters of Malonic Acids, Tetrahe Second step, Stoichiometric amounts of a diamine, preferably dron Letters Nos. 32, p. 2721–2723, 1994. an orthophenylene diamine, are added to the macro linker G. A. Fletcher and J. H. Jones, A List of Amino-Acid intermediate in the presence of a coupling agent and heat. Derivatives Which Are Useful in Peptide Synthesis, Int. J. This Second double coupling reaction, is allowed to proceed Peptide Protein Res. 4, 1972, 347–371, Jun. 10, 1972. for a period of time Sufficient to produce a macrocyclic Jose M. Workman, Routes to Multimetallic High Oxidation tetraamido compound. The Substituent groups on the C. or B State Transition Metal Complexes, Carnegie Mellon Uni amino carboxylic acid, the malonate, and the aryl diamine versity, Mellon College of Science, Jul. 23, 1992. may all be Selectively varied So that the resulting tetraamido Terrence J. Collins, Designing Ligands for Oxidizing Com macrocycle can be tailored to Specific desired end uses. The plexes, Department of Chemistry, Carnegie Mellon Univer macrocyclic tetraamide ligand may then be complexed with sity, Accounts of Chemical Research, 1994, 27, p. 279. a metal, Such as a transition metal, and preferably the middle Masaru Nakamura, Mitsuko Toda and Hiroko Saito, Fluo and later transition metals, to form a robust chelate complex rimetric Determination of Aromatuc Aldehydes With 4,5-Dimethoxyl-1,2-Diaminobenzene, Analytica Chimica Suitable for catalyzing oxidation reactions. Acta, 134 (1982) 39-45. 19 Claims, 3 Drawing Sheets U.S. Patent Apr. 18, 2000 Sheet 1 of 3 6,051,704 U.S. Patent Apr. 18, 2000 Sheet 2 of 3 6,051,704 Oxidized Product Reducing Substrate FIG. 4 U.S. Patent Apr. 18, 2000 Sheet 3 of 3 6,051,704 N (i) BuLi, FeCl2, C -o THF, -108°C sus C HHN (ii) O2, 25°C C NFeN-a2 Do?O SN Oy (iii)8 (Eta N]+, C (JNSO O DOWex 2 (NH4)2Ce(NO3)6 (i) AgBF4/MeCN CHCI 2Ol2 (ii) H2O recryst. C OH2 O N 4 3 H2O, CN CH3CN, TBHP N O O. VS C NFs. O ONSW Y. C O O 6,051,704 1 2 SYNTHESIS OF MACROCYCLC Substrate, high oxidation State transition metal complexes TETRAAMIDO-N LIGANDS tend to exhibit low oxidative selectivity and will instead oxidize any available Substrate. Since the ligand comple This invention was made in part with funding from the ment is available in high local concentration as a possible National Institute of Health, Contract No. GM-44867 and Substrate, oxidative degradation of the ligand complement the National Science Foundation, Contract No. has been a formidable impediment to obtaining long lived CHE9319505. The U.S. government may have rights in this invention. oxidation catalysts in the absence of a Stabilizing matrix. BACKGROUND OF THE INVENTION 1O Collins, T. J., “Designing Ligands for Oxidizing 1. Field of the Invention Complexes,” Accounts of Chemical Research, 279, Vol. 27, The invention relates to Synthetic methods for producing No. 9 (1994), describes a design oriented approach for macrocyclic compounds, and more particularly, to Synthetic obtaining ligands that are resistant to oxidative degradation methods for producing tetraamido macrocyclic ligands and 15 when coordinated to highly oxidizing metal centers. Several metal chelate complexes as pre catalysts for oxidation diamido-N-diphenoxido and diamido-N-alkoxido acyclic reactions. chelate compounds and macrocyclic tetraamido-N chelate 2. Description of the Invention Background compounds are described in the Collins Accounts of Chemi Complexes of high oxidation State transition metals are cal Research article. known to function as Oxidants in numerous biological reac tions under the influence of a protein matrix and in recent An azide based Synthetic route to macrocyclic tetraamido years a widespread interest in understanding the mechanism ligands is described in Uffelman, E. S., Ph.D. Thesis, of action and the reactivity of certain monooxygenase cata 25 California Institute of Technology, (1992). Synthesis of the lysts has developed. However, in the absence of a protein tetraamido ligands via the azide based route developed by matrix to direct the oxidizing power towards a specific Uffelman proceeds generally as follows: CHCl2, EtN He O S. 2 nn + 2-Diamine B Br Br Br NaN, EtOH, H2O A Xs s Schiff Base Pd/C/H. EtOH -- 1.1 MHBF4, EtOH 2. NaOH, CH2Cl2 Cl C He CHCl2, EtN 6,051,704 3 Synthesis of an aryl bridged tetraamido ligand via the azide based route proceeds as follows: O X NH2 X Br Br CHCl2, EtN X NH2 X NH Br O 2 N NaN, EtOH X H2O, A X X = H, Me, OMe 7 III.iii. The yield of the azide based method is about 25% for the yield of the desired tetraamido ligand is comparatively low. final ring closing step but only about 5-10% for the com 6 O Furthermore, the azide based method produces high energy bined Sequence of StepS Starting from the diamine. This intermediates. method generates new C-N bonds via formation of azide There is a need for an alternative method of producing intermediates. The generation of the C-N bonds, however, tetraamido ligands. There is also a need to improve the yield 6 5 of Such ligands. Finally, there is a need for a method of is not very effective, at least as to yield. With each step of producing tetraamido ligands that are resistant to oxidative the process, the yield is reduced further so that the overall degradation and in which the various Substituent groups can 6,051,704 S 6 be controlled to tailor the ligands and the metallo complexes diamine may all be selectively varied So that the resulting they form for Specific end uses. tetraamido macrocycle can be tailored to Specific desired end uses. This highly efficient Streamlined Synthesis not only SUMMARY OF THE INVENTION tolerates a comparatively wide range of functional groups, The foregoing needs are met by the method of the present but also employs relatively low cost reagents and is com invention and the compounds produced thereby. This patible with large Scale operation, all of which are highly method provides powerful new synthetic routes for the desirable Synthetic features. preparation of macrocyclic amido-N donor ligands, and Variation of the Substituents has little or no effect on the particularly those with oxidatively robust substituents. The methodology. In varying the macrocycle, however, it is primary method of the present invention Substantially important to preserve the amide framework. The macrocycle increases the yield, and reduces the number of Steps, as well will be made up of 5- and 6-membered rings, in a 5.5.5.5 as the time and the cost of the process as compared to the pattern, a 5.5,5,6, pattern, a 5,6,5,6 pattern, a 5,5,6,6, pattern, a 5,6,6,6 pattern, or a 6,6,6,6 ring pattern which will be prior art azide method. Importantly, the new Synthetic 15 method reduces the hazards inherent to the azide method due described in more detail below. to that methods high energy intermediates.
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