VOLUME 8, N0. 3, 2001
`
`ISSN 0793-0291
`
`PM
`
`Editor
`
`PROF. MARCEL GIELEN
`
`© 2001 FREUND PUBLISHING HOUSE LTI).
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`
`METAL-
`
`BASED
`
`DRUGS
`
`Tl
`1’ Km 4”‘;
`
`/7
`
`-1
`
`-
`
`\
`
`,:\
`
`\ F,
`
`l
`M
`
`2 , _,_\ Q
`_/J‘\ /2\ ‘,/”“\
`l_,. \.
`a ti cl pi e /2 wi mi
`
`Metal-Based Drugs, 8 (2001), 119 - 124
`
`ACTIVITY OF Pt(||) AND Flu(I|I TFIIAZOLOPYFIIMIDINE COMPLEXES AGAINST
`PARASITES OF THE 6 /VUS LE/SHMA/V/A, 7'/-?I’PA/VOSOMASAND
`PHI’7'0/I/I0/VAS
`
`Juan M. Salas*,‘ Miguel Quiros,‘ Mohammad Abul Haj,‘ Rosa Magan,2
`Clotilde Mari’n,9 Manuel Sa'nchez—Moreno2 and Rene’ Faurea
`
`"2 Universidad de Granada. 18071 Granada, Spain
`3 Université Claude Bernard Lyon 1, 69622 Villeurbanne, France
`
`The synthesis and characterization of two Pt II) complexes with the can
`isom_er_ic
`li ands 4,5-dih d.ro-5-oxo- 1 2,4] ria_zolo—[1,5-
`alpyrimidine %?HtpO) and 4, -dihydro-7-oxo-I1,2,4]-triazolo-[1,5- ,,
`
`apyrimidine HtpO) are described, as well as a Ru(l|l) comp|ex,,,=v
`with 7HtpO. he crystal structure of ci_s-[PtCl (7HtpO)2].2H O has
`been solved by X-ray diffraction analysis. In vifro activity oft e new
`isolated complexes against the epimastigote form of T. cruzi,
`procyclic form ofT. b. brucei and promastr ote form of L. donnovani
`and P. characias has also been studie . The three complexes
`markedly affect the growth of the parasites and none of them shows
`cytotoxicity against macrophage of the J774.2 line at the heaviest
`dosaes use .
`
`Metal-Based Drus, 8 2001 , 125 - 136
`INTERACTION OF RUTHEN|UM(II)-DIPYRIDOPHENAZINE COMPLEXES WITH
`CT-DNA: EFFECTS OF THE POLYTHIOETHER ANCILLARY LIGANDS
`Teresa M. Santos“, Joao Madureirat, Brian J. Goodfellowt, Michael G. B. Drewz,
`Julio Pedrosa de Jesus‘, and Vitor Felix‘
`‘Department of Chemistry, University of Aveiro.
`Campus Universitario de Santiago, 3810-1 93 Aveiro, Portu al, te_resa@dq.ua6)t
`2Department of Chemistry, The University. Whiteknights,
`eading, RG6 6A , UK
`
`2 ([9]aneS,=1,4,7-
`1 and [[Fiu(é12]aneS4)(dppz) Cl
`The complexes [Ftu([9 aneS§)(dppz C|]Cl
`trithiaciclononane and 1
`ane 4=1,4,
`,10-tetrathiacic odo ecane) were synt esised and fu||y'char_ac-
`tensed. These complexes elong to a small family of dipyridofihenazine complexes with non-polypyridyl
`ancillary ligands. Interaction studies of these complexes wit CT-DNA (lJV/Vis titrations, steady-state
`emission and thermal denaturation) revealed their high affinit
`for DNA.
`Intercalation constants
`determinedbyUV/Vistitrationsareofthesameorderofma nitude(1 6)_asotherdppzmetallointercalators,
`namely [Ru(l )(bpy)2dppz 2*. Differences between 1 and were identified by steady—state emission and
`thermal denaturation stu ies. Emission results are in accordance with structural data, which indicate no
`geometric distortions and different donor and/or acceptor ligand abilities affect luminescence. The
`possibility of non—covalent interactions between ancillary ligands and nucleobases by van der Waals
`contacts and H-bridges is discussed. Furthermore,‘ complex 1 under oes a uation under intra—cellula
`conditions and _an equilibrium with the aquated form 1' is attained.
`his be aviour may increase the
`diversity of available interaction modes.
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`
`, 137 - 143
`I Metl-Based Dru
`TRANSITION METAL ION COMPLEXES OF SCHIFF-BASES.
`
`SYNTHESIS, CHARACTERIZATION AND ANTIBACTERIAL PROPERTIES
`Zahid H. Chohan“, Asifa Munawal and Claudiu T. Supurang
`_
`1 Department of Chemistry, lslamia University, _Bah_awalpur, Pakistan
`2 Universita degli Studi, Dipartimento di C imica, Laboratorio di Chimica lnorganica e Bioinorganica,
`Via Gino Capponi 7, I-50121 Florence, Italy
`Some novel transition metal Co(ll), Cu(ll% Ni(ll) and Zn(ll)] com-
`pkexes of subdsgtutald payritldine
`chiflfibajses lave lluajen prfipared and
`c aracterize
`yp sica,s ectra an ana tica
`ata.
`es nt e-
`sized Schitf—bases/ act as deprotonate/d tridentate foyr
`the
`complexation reaction with Co(l|),
`'(II) and Zn(|l) ions. The new
`corn ounds. possessing the
`eneral formula 2[M(Lg2] wher4e
`[M= o(ll), Cu( ), Ni(Il) and Zn(ll and HL=HL , HL , HL and HLI
`show an octrahledral graoréiefilryflln ordertg ehvaluate tae effefit of ngeta
`ions uponc e ation,t e c I
`asesan t eircom exes ave een
`sgregnedhior ar/i_tibEi‘cte;i7a|/ activity against thejstaraainsdsuch as
`
`seu omonas
`fap yocaccus aureus, an
`so er/0 /a 00/,
`aeruginosa. The complexed Schiff bases have shown to be more
`antibacterial a ainst one more bacterial species as compared to
`uncomplexed chit—bases.
`
`Metal-Based Drugs, 8 (2001), 145 - 148
`NEW BORON ANALOGUES OF PYROPHOSPHATES AND
`DEOXYNUCLEOSIDE BORANOPHOSPHATES
`Kamesh Vyakaranaml, Geeta Rana‘, Nara an S. Hosmane“,
`and Bernard F. Spielvogel "2
`‘ Department of Chemistry and Biochemistgyé Northern Illinois University,
`DeKalb, IL 60115-28
`USA
`2 Metallo-Biotech International, |nc., 663 Teal Court, DeKalb, IL 60115-6201, USA
`
`Tetraethyldicyanoborane
`pyrophosphate
`(2)
`and
`3’-
`(diethylphosphite-cyanoborano)-5’-
`dimethoxytrityl-N4—benzoyl-
`deoxycytidine (3) have been
`0
`OH
`OH
`synthesized in 70% and 76% yields,
`I
`|
`I
`respectively. The compatibility ofthe
`substituted boranophosphates with EtO""P'—O:P:OET NCH2 B‘_P"'OEt
`common protecting groups is
`l
`l
`hereby demonstrated.
`BHZCN
`GET
`
`DM-l-_
`
`H
`
`BHZCN
`
`Metal-Based Drus, 8 2001 , 149 - 158
`
`ANTIANDROGEN AND ANTIMICROBIAL ASPECTS OF COORDINATION
`COMPOUNDS OF PALLAD|UM(lI), PLAT|NUM(I|) AND LEAD(||)
`R.V. Singh“, SC. Joshiz, Shalini Kulshrestha‘, Pooja Nagpal‘ and Anil Bansal‘
`‘Department of Chemistry, 2Department of Zoology, University of Rajasthan, Jaipur—302004, India
`The complexes M(MaL”l(R )]Cl, and [Pb(l\[laL")(Ra)X MM = Pd" or Pt“ and X : Cl or NO have been
`synthesized b ‘the reac ioris ormacrocyclic ligan s E
`aL”) with metal salts and ditferen diamines in
`1:1 :1 molar ra IO in methanol. The complexes were characterized b elemental anal ses m olecular
`wei htdeterminations,conductivity measurements, IR, ‘H NMR,‘3C MR, ‘95PtNMR,
`‘7PbNMR,XRD
`an electronic spectral studies.
`The macrocyclic ligand coordinates through thefourazomethine
`R2
`nitrogen atoms which are brid ed by benzil moieties. IR spectra
`su gest that
`the pyridine ni rogen is not coordinatin . The
`a adium and
`latinum com lexes exhibit
`tetracoor inated
`gquareplanarlggometry, wherpeas a hexacoordinated octahe—
`dral geometry IS sug ested forlead com lexes. The complexes
`havebeen evaluate for their antimicro ial effects on di ferent
`species of pathogenic fungi and bacteria. The testicular sperm
`density, testicular sperm morphologjy aperm motiIi_ty, density of
`cauda epididymal spermatozoa an te ility in mating trails and
`biochemical _arameters of reproductive organs have been ex-
`amined and iscussed.
`
`X
`N
`N
`/ \ / \
`
`CeH5
`
`H5c6
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`
`Metal-Based Drus, 7 2000 , 159 - 164
`CHARACTERIZATION AND ANTIMICROBIAL ACTIVITY OF
`ERBIUM(I||) COMPLEXES
`S. B. Jagtap‘, N. N.Patil*2,B. P.Kapadnis*9 and B. A. Kulkarni‘
`University of Pune, Pune - 411 007. lndia ‘Department of Chemistry 2Department of Microbiology
`<bpkap@unipune.ernet.in>
`of 2-hydroxy—1,4-naphthoquinone~1-
`Erbium(lll) metal complexes
`oxime and their C-3 substituted derivatives were synthesized. The
`complexes were characterized by melting point, elemental analysis, IR
`and ‘HNMR spectroscopy and magnetic susceptibility. The antimicro—
`bial activity of these complexes was determined by well diffusion
`method against the target microorganisms, Sfap/7y/ococcus aureus,
`/Ya/71‘/70/770/7as campesfr/19, Pseudomonas aerug//703a, Ca/70’/'0’a
`a/b/ca/vsand Asperg///L/5/7/gen The antimicrobial activity of ligands and
`their complexes was compared. it was seen that the ligands are more
`antifungal than antibacterial and the antimicrobial activity of the ligands
`reduced on complexation with erbium(lll).
`
`HO
`\
`
`N
`J
`
`Er)3
`\
`O
`
`Metal-Based Drugs, 7 (2000), 165 - 169
`SSYNTHESIS, CHARACTERIZATION AND IN VITRO ANTIFUNGAL EF-
`FECT OF SOME BUTYLTIN(IV) N-SUBSTITUTED 2-AMINOETHANETHIOLATES
`A. Smicka‘, V. Buchtag and K. Handlir*‘
`1 Department of General and Inorganic Chemistrg, Faculty of Chemical Technology, University of
`Pardubice, nam. Cs. Legii 565, 5 2 10 Pardubice, Czech Republic
`<ales.smicka@upce.cz>, <karel.handlir@u8ce.cz>
`_
`_
`9 Department of Biolo ical and Medical Sciences, Faculty of
`harmacy, Charles_University,
`Heyrovskeho 12 3, 500 05 Hradec Kralove, Czech Republic <buchta@faf.cuni.cz>
`Six new N—substituted di- and tributyltin
`cysteaminates 2—amino_ethanthiolates have been
`ltl‘iEaa;‘E‘éa1?§sEoS’aiifi'£F;§Seb3oH?‘Sinai’? $2
`.
`X
`considerable //7 i//1)‘/r0 fungicidal ac ivity against se—
`lected types of fungi (Ca/70’/‘c/a a/b/Ca/75, Cano’/'0’a
`/rrc,/5e/, Ca/70’/da
`rap ‘ca//5, Ca/70’/'0’a g/abrafa,
`7'r/0/,70,s,00r0/7 be/ge///; Asperg///us /um/galus,
`/4175/0’/a
`/)
`c0r+/r/177b//‘era,
`7'r/'0/lg /7}/[fin
`me/7/.3 rap res.
`is activit
`is com ara etot e
`commgnly u}s/,ed)drugs. The IIelationIs3hip between
`structure and fun icidal activit
`is discussed.
`
`11
`1
`2 n
`1 D
`‘
`
`=3;X:-CH2-
`;3;X=_o-
`
`=3;X -'— -NCH3
`
`/
`\
`/\,N X
`BU”Sn S U
`
`Metal-Based Dru s, 7
`
`COPPER(|I) ACYLHYDRAZINATES.
`THEIR SYNTHESIS AND CHARACTERIZATION
`Zahid H. Chohan*I, M. A. Farooq‘ and Claudiu T. Supurang
`.
`‘Department of Chemistry, lslamia Universit
`, Bahawalpur, Pakistan
`Laboratorio di Chimica lnorganica e Bioinorganica,
`niversita degii Studi, Via Gino Capponi
`7, I-50121, Firenze, Italy
`
`2
`
`Acylhydrazine derived furan I and thienyl
`Sc iff bases and their Cu(l) complexes
`have been pre ared and characterized on
`the basis of t eir physical, spectral and
`analytical data. The preferred enolic form
`of the Schiff base function as a tetradentate
`ligand during coordination to the metal ion
`gelding a square planar complex. The
`chiff bases and their complexes with dif-
`ferent anions were tested for their antibac-
`terialactivitya ainstbacterials ecies such
`as Est:/7er/c /a co//; S/ap 7}//ococcus
`aurez/5, Pseudomonas aerug//705a a‘/70’
`/(/abs/e//a pneu/770/7ae..
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`
`Ajeful Based’ D]~l(gs
`
`This material may be protected by Copyright law (Title 17 U.S. Code)
`
`I/0/g 8‘ /’\/r. 3, I
`
`NEW BORON ANALOGUES OF PYROPHOSPHATES AND
`DEOXYNUCLEOSIDE BORANOPHOSPHATES
`
`~
`Kamesh Vyakaranam‘, Geeta Ranal. Narayan S. Hosmane*1, and Bernard F. Spie1Vogel*
`
`1.2
`
`' Depaitmept of Chemistry and Biochemistry, Northern Illinois University, DeKa1b, 1L 601 15-2862, USA.
`‘ Metallo-Biotech International, 1iic.. 663 Teal Court, DeKalb, IL 60115-6201, USA
`
`ABSTRACT
`
`Tetraethyldicyanoborane pyrophosphate (2) and 3‘-(diethylphosphite—cyanoborano)-5’-dimethoxytrityl-N‘-
`benzoyl-deoxycytidine (3) have been synthesized in 70% and 76% yields, respectively. The compatibility of
`the substituted boranophosphates with common protecting groups is hereby demonstrated.
`
`Boron containing biologically active compounds. such as nucleosides and nucleotides "6 and amino acids M
`are important due to their potential therapeutic activity, research and diaonostic applications. Many boron
`containing compounds have shown promising activity as anticancer,“ H‘
`'3 antiinflammatory,]3 and
`antiosteoporotic “agents. Oligonucleotides in which a non-bridging oxygen atom is replaced by a borane
`(BH3) group are a very important class ofmoditied nucleic acids. 1‘
`3‘ “"6 The BH3 group is isoelectronic with
`oxygen in natural oligonucleotides and isoelectronic and isostructural with the oligonucleotide methyl
`phosphonates, which are nuclease resistant. On the other hand,
`the ot—borano triphosphates are good
`substrates for DNA polymerases and inpor oration of boranophosphates into DNA causes an increase in the
`resistance to exo— and endonucleases " I
`“ as compared to non—modified DNA. There are also notable
`.
`.
`s
`.
`.
`,
`.
`7
`.
`.
`.
`7
`applications ot the ot-borano triphosphates in PLR sequencing ' 3 and nucleic acid detection] b
`
`Figure 1. Isoelectronic Nucleic Acid Backbones
`
`ii
`
`Boranophosphate
`
`Methylphosphonate
`
`Although considerable effort and progress has been made with the boranophosphate linkage,
`numerous limitations with this moiety still exist, especially in chemical syntheses. Thus, the highly reducing
`borane group causes base degradation and incompatibility with commonly used protecting groups in
`modified oligonucleotide synthesis.3‘“)‘ '8“ Likewise, the BH3 moiety has severe toxicity implications.
`' We
`have been intensively investigating the attachment of substituted boranes such as BH3X, where X : COOR,
`C(O)NR’H, CN, etc.,
`to phosphorus in biologically important molecules. Here we report the use of
`substituted boranes in the syntheses ofboronated pyrophosphates and nucleic acids which promises to greatly
`expand the scope ofthis class ofnucleic acids.
`Reaction of the potassium saltzo of diethylphosphite-cyanoborane 1 with methanesulfonyl chloride
`gave tetraethyldicyanoborane pyrophosphate 2 as shown in Scheme 1. Purification was achieved by column
`chromatography using ethyl acetate as an eluent. The yields range from 65-71% 31. Analysis by “P NMR
`spectroscopy showed a quartet of triplet at 5 80.21 ppm corresponding to the cyanoborane phosphate group.
`The "B NMR spectrum of2 contained a doublet of triplet at 5 — 40.58 ppm corresponding to cyanoborane
`phosphate group. [R spectrum of the purified product showed a broad band at 2409 cm‘ corresponding to B-
`H stretch and a sharp peak at 2361 cm" consistent with CN stretch.
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`
`Narayan S. Hosmane er al.
`
`New Boron Analogues of Pyrop/iosp/tales and
`De0xy11z1c/eoside B0/'an0p/705p/rates
`
`REACTION SCHEME 1:
`
`Brz /DME
`
`(OEUSP
`
`Nai3H;,CN——> (BH2C-\l)x"DI:’
`
`Eto-——[>———oEt
`
`BH2X
`
`Et
`
`pEt
`pEt
`plat
`MeSO3Cl
`Eto—- —oK —-——> Eto—-—— —-o--P-oEt
`F
`CH3CN
`BHZX
`
`BHZX
`
`BHZX
`
`1 X=CN
`
`2 X=CN
`
`REACTION SCHEME 2:
`
`C/Bz
`
`.
`(l)t-BuL1 THF
`——e——->—
`(2) 2 /riir
`(3) Water
`
`H
`
`p
`XHZB--P--C)Et
`
`(4) Column chromatography
`
`OE‘
`
`The preparation of K’ (RO)3PBH;,' salt and analogous tetramethyl-boranopyrophosphate was previously
`reported by [mamato ez. al. 22, and demonstrated to have good versatility in the preparation of
`boranophosphate compounds. However, these species may still be of limited use because of the presence of
`highly reducing BH3 moiety. Convincing evidence that sziibstitmed boranes with less reducing power can
`mitigate many of the problems caused by the BH3 group is demonstrated by the synthesis of 3.
`In this
`instance, the 5’-trityl protected group is retained in the synthesis whereas with borane unit, BH3,
`it
`is
`completely removed. 3"“ Thus, the reaction of5’—protected 2’-deoxycytidine, Benzoyl (B2), dimethoxytrityl
`(DMT) deoxycytidine, with pyrophosphate 2 (Scheme 2), followed by evaporation ofthe solvent resulted in
`the formation of 3’-(diethylphosphite-cyanoborano)- 5’-dimethoxytrityl-N4-benzoyI-deoxycytidine 3. This
`crude product was purified by flash chromatography and obtained in 75% yield (by ‘H NMR) 23. Analysis by
`“P NMR spectroscopy showed a quartet of triplet at 5 68.12 ppm corresponding to the cyanoborane
`
`146
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`
`Metal Based Drugs
`
`V0], 8, N;-, 3, 2001
`
`phosphate group. The “B NMR spectrum of2 contained a doublet oftriplet at 5 —~ 39.63 ppm corresponding
`to cyanoborane phosphate group. IR spectrum of the purified product showed two broad bands at 2762 and
`2701 cm'], corresponding to B-H stretch, and a sharp peak at 2295 cm" is consistent with CN stretch. The
`DMT protecting group and boranophosphate were incompatible in previous synthetic proeedL11‘es.3“"8
`However, with the use of the less reducing cyanoborane, the DMT nucleoside was isolated in 75% yield
`using the procedure described here. Substituted boranes are less reducing than BH3 moiety and should also
`inhibit the base degradation. In fact, cyanoborane adducts of various N positions of purine and pyrimidine
`nucleosides have been prepared with the bases not reduced or degraded. M’)
`Thus, in View ofthe great importance of phosphate moieties (pyrophosphates. nucleic acids, etc.) in
`biological processes,
`the availability of boronated phosphates, such as 2 and 3,
`is expected to be of
`considerable interest. Work on a variety of such species is currently underway in our laboratories.
`
`ACKNOWLEDGMENT. This work was supported by grants from the National Science Foundation (CHE-
`9988045), the donors ofthe Petroleum Research Fund, administered by the American Chemical Society, and
`Northern Illinois University through Presidential Research Professorship (to NSH).
`
`REFERENCES
`
`* Corresponding author, Fax (815)753-4802, email: nhosmaneiYTIniu.edu
`l. Hasan, A.; Li, H.; Tomasz, 1.; Shaw, B.R.; Nucl. Ac1'a’Res. 1996, 2-/, 2150-2157.
`2.
`(a) Li, H.; Porter, K.; Huang, F.; Shaw, B.R.; Nucl. Acid Res. 1995, 23, 4495-4501. (b) Sood, A.;
`Shaw, B.R.; Spielvogel, B.F.; J. Am. Chem. Soc. 1990, 112, 9000-9001. (C) Sood, A.; Spielvogel.
`B.F.; Shaw, B.R.; J. Am. Chem. Soc. 1989, II], 9234-9235.
`Spielvogel, B.F.; Sood, A.; Shaw, B.R.; Hall, I.H.; Fairchild, R. G.; Laster, B.H.;
`Progress in Neutron Capture therapy for Cancer 1992, 21 1-213.
`Shaw; B.R.; Madison, 1.; Sood, A.; Spielvogel, B.F.; Methods in Mol. Biol. 1993,20, 225-243.
`Kane, R.R.; Drechsel, K.; Hawthorne, M.F.; J. Am. Chem. Soc. 1993, /15, 8853-8854.
`Spielvogel, B.F.; Sood, A.; Shaw, B.R.; Hall, I.H.; Pure Appl. Chem. 1991, 63. 415-418.
`Spielvogel, B.F.; Sood, A.; Tomasz, 1.; Shaw, B.R.; Karthikeyan, S.; Neutron Capture The/'. 1993,
`361-365.
`
`Gordon, C.;
`
`Kane, R. R.; Pack, R. H.; Hawthorne, M.F.; J. Org. Chem. 1993. 58, 991-992.
`Hall, I.H.; Hall, E. S.; Chi, L.; Shaw.B. R.; Sood, A.; Spielvogel, B. F.; Anticancer Res. 1992, 12,
`1091-1098;
`. Sood, A.; Spielvogel, B.F.; Shaw B.R.; Carlton, L.D.; Burnham, B.S.; Hall, E.S. Hall. I.H.; ibid.
`1992, 12, 335-334.
`.
`. Sood, A.; Shaw, B.R.; Spielvogel, B.F.; Hall, E.S.; Chi, L.K.; and hall, I.H.;
`833-838.
`
`Pharmazie 1992, -/7,
`
`. Spielvogel, B.F.; Sood, A.; Shaw, B.R.; Hall, I.H.; Curr. Top. Chem. Boron Proc. Int. Meet. Boron
`Chem, 3"‘, 1994, pp. 193-193.
`. Rajendran, K.G.; Burnham, B.S.; Chen, S.Y.; Sood, A.; Spielvogel, B. F.; Shaw, B.R.; Hall. I.H. J.
`Pharm. Sci. 1994, 83, 1391-1395.
`Tomasz, 1.; Shaw. B.R.; Porter, K.W.; Spielvogel, B.F.; Sood, A. Angew. Chem, Int. Ed. Engl.
`1992, 31,1373—1375.
`. Krzyzanowska, B. K.; He, K.; Hasan, A.; Shaw, B.R. T.<:tral7edron 1998, 54. 5119-5128.
`. He, K.; Hasan, A.; Krzyanowska, B. K.; Shaw, B.R. J. ()1 g. Chem. 1998, 63. 5769-5773.
`.
`(a) Porter, K. W.; Briley, 1.D.; Shaw, B.R.; Nucleic Acid Res. 1997, 25, 1611-1617. (b) Spielvogel,
`B. F.; Powell, W.; Sood, A. Main Group Metal Chemistry, 1996, [9, 699-704.
`(a) Higson, A. P.; Sierzchala, A.; Brummel, H.; Zhao, Z.; Caruthers, M. H. Tetrahedron Letters,
`1998, 39, 3899-3902. (b) Levinskas, G. 1., Boron, Metalloboron compounds and Boranes, Chap. 8,
`lnterscierzce, 1964.
`(a) Eriksson, B.; Oberg, B.; Wahren, B. Biochim. Biophys. Acta 1982, 696, 115-123. (b) Eriksson,
`B.; Larsson, A.; Helgstrand, E.; Johansson, N. (1.; Oberg, B. Biochim. Biophys. Acta 1980, 607, 53-
`64. (c) Eriksson, B.; Tao, P. Z.; Wahren, B.; Oberg. B. Proc. Int. Confr. Chemothe/2; 13th, 1983, 6,
`1 14/'29-1 14/32.
`
`.
`
`.
`
`. Sood, A.; Sood, C.K.; Hall, I.H.; Spielvogel, B.F. Tetrahedron, 1991, 47, 6915-6930.
`potassium salt of
`. Methanesulfonyl chloride (0.96g, 8.34mrnol) was added to a solution of the
`diethylphosphite-cyanoborane (3.0g, 13.9mmol) in acetonitrile (50 mL) at 00C and the mixture was
`stirred at room temperature for 4 h. The precipitated solid was removed by filtration, and the filtrate
`was concentrated under reduced pressure. The residual oil was passed through a short column of
`silica gel with ethyl acetate to give 3.25g (70%) compound 2 as a colorless oil.
`'H NMR (200 MHZ;
`DMSO reference to TMS) 5 1.20 (sh, t, 3H), 3.35 (sh "tn, 2H); “B NMR (54.21 MHZ; DMSO
`reference to BF3.OEt2)5 -40.58 ((1 oft, 1./B,» 1 160.4 Hz); i’C NMR (50.32 MHz; DMSO reference to
`TMS) 8 16.9 (d of d, ’Jpc = 4.0 Hz, C113; 57.71, d ofd, 2.11%; = 4.9112, CH3). "P NMR (81.01 MHZ;
`
`147
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`Nara an S. Hosmane et a/.
`J’
`
`New Boron Ana/0 1/es 0 P 11:0 7/ms hates and
`8’
`.
`J
`I
`/7
`Deoxyrzztc/e0s1‘de Boranophasp/zates
`
`.
`
`DMSO reference to H3PO4) 5 80.21 (q of t, Jpg = 163 Hz);1R(KBr pellet) 2409, 2361 v(Bl'l); 2209
`v(CN). Anal. Calcd for CmH;4P3O3B3N3: C, 35.74; H. 7.2; N, 8.33. Found: C, 35.01; H, 7.9; N,
`8.56. This compound decomposes at 120 °C.
`_
`lmamoto. T.; 1.; Nagato, E.; Wada, Y.; Masuda. H.; Yamaguchi, K.; Uchimaru, T. J. Am. Chem.
`Soc. 1997, /19, 9925-9926.
`. Benzoyl-Dimethoxytrity1-deoxycytidine (250 mg, O.4mmol) was dissolved in 15 mL ofTHF and the
`solution was cooled to -78 0C. After 30 minutes, t—BuLi (1.0mL, 1.25mmol) was added to the
`reaction mixture and the reaction was carried out for 30 minutes. Tetraethyldicyanoborane
`pyrophosphate (200mg, O.5m1nol) dissolved in 10mL of THF was added to the solution and reaction
`continued for 18 h. The solvent was evaporated under reduced pressure. To the crude extract, 25 mL
`of water was added and solution was stirred for 5 h. The solid was filtered off and purified by
`chromatography using ethyl acetate/' hexane (9:1) to give O.24g (75.7%) ofcompound 3. ‘ll NMR
`(200 MHZ; DMSO reference to TMS) 5 8.23 (m, 5H, Ar—H), 7.69(br. 13H. Ar-H), 7.65 (cl, 2H. H-5,
`H-6), 6.18 (t, 1H, H-1’), 2.21, 2.15 (m, 2H. H-2’), 4.0 (m. 1H. H-3’), 5.37 (m, 1H, H-4’), 3.67, 4.05
`(m, 2H. H-5’). 3.95 (q, 4H), 1.3fl(t, 6H); “B NMR (64.21 MHz. DMSO reference to BF_~..OEt3) 5 —
`39.63 (d oft, ‘.15.. = 178.6 Hz ); ~‘ P NMR (81.10 MHZ; DMSO reference to H;.Po.) 5 68.12 (q of 1,
`Jpg = l63Hz). IR (KBr pellet) 2762, 2701 \/(BH); 2295 V(CN). Anal. Calcd for C.;3l'l4(,O9N4BP: C.
`63.63; H. 5.80; N, 7.07. Found: C, 62.89; 1-1, 6.10; N. 6.42.
`
`Received: May 28, 2001 —- Accepted: June 20, 2001 —
`Accepted in publishable format: June 20, 2001
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