Click Chemistry. Rafał Loska Literature Seminar

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1 Click Chemistry Rafał Loska Literature Seminar

2 The most fundamental and lasting objective of synthesis is not production of new compounds, but production of properties. George S. Hammond, orris Award Lecture, 1968

3 The Concept of Click Chemistry Traditional natural product synthesis construction of large carbon skeletons complicated protective groups schemes expensive; low final yield after a long linear synthesis often difficult to scale up, especially for Click Chemistry modular approach readily available building blocks, often natural compounds fast, efficient reactions to connect them formation of carbon-heteroatom bonds C-C bond forming steps no protection groups difficult to modify the lead structure and perform SAR studies - P H H H H H - P Discodermolide secondary metabolite with anticancer properties H R R H Polipeptides Polinucleotides H H H H H H H H ligosaccarides

4 Click Reactions Criteria for useful click reactions : wide scope very high yield selectivity simple conditions insensitive to oxygen and water, no need for very low or high temperatures readily available starting materials no solvent or a benign solvent, or an easily removed solvent simple isolation of the product crystallization or distillation, no chromatography stability of the new bond, for example under physiological conditions in the case of drugs kinetically controlled, exothermic (at least 20 kcal/mol), very selective H. C. Kolb, M. G. inn, K. B. Sharpless, Angew. Chem. Int. Ed. 2001, 40, 2004

5 Click Reactions R' + - Cu(I) R' + u: 1,3-dipolar cycloaddition Diels-Alder reaction + R'' R'' R X X R' u R' X X + R X =, -R'', S + -R'' + H 2 X R X R nucleophilic opening of small rings X =, H oxime ethers, hydrazones etc. R' SH + R' S R'' R' + H 2 R'' H R' R'' R'' radical addition of thioles to alkenes (click thio-ene chemistry) condensation with carbonyl group

6 Click Reactions R' + - Cu(I) R' + u: 1,3-dipolar cycloaddition Diels-Alder reaction + R'' R'' R X X R' u R' X X + R X =, -R'', S + -R'' + H 2 X R X R nucleophilic opening of small rings X =, H oxime ethers, hydrazones etc. R' SH + R' S R'' R' + H 2 R'' H R' R'' R'' radical addition of thioles to alkenes (click thio-ene chemistry) condensation with carbonyl group

7 1,3-Dipolar Cycloaddition of Azides and Alkynes R R 2 R 1 R 2 1,4-disubstituted 1,2,3-triazole orthogonality of azide and alkyne function to a wide variety of other functional groups and reaction conditions neither azide nor terminal alkyne functional groups are present in natural systems both substrates available by many synthetic routes complete 1,4 selectivity in Cu catalyzed reaction reaction possible in water no side products a perfectly atom-economic process H. C. Kolb, M. G. inn, K. B. Sharpless, Angew. Chem. Int. Ed. 2001, 40, 2004 M. ldal, C. W. Tornøe, Chem. Rev. 2008, 108, 2952 V. D. Bock, H. Hiemstra, J. H. van Maarseveen, Eur. J. rg. Chem. 2006, 51 J. D. Moses, A. D. Moorhouse, Chem. Soc. Rev. 2007, 36, 1249 J.-. Lutz. Angew. Chem. Int. Ed. 2007, 46, 1018 C. R. Becer, R. Hoogenboom, U. S. Schubert, Angew. Chem. Int. Ed. 2009, 48, 4900 R. K. Iha, K. L. Wooley, A. M. ystrom, D. J. Burke, M. J. Kade, C. J. Hawker, Chem. Rev. 2009, 109, 5620

8 Preparation of Azides a 3 R LG R 3 H + 3 or 2 H a 3 H 3 R' R'' R' R'' 2 + a ICl, a 3 I 3 R' R'' R' R'' - 2 R' R'' I 3 R' I 3 R'' base -HI R' 3 R'' 3 R' H R'' H 3 DAED R' 3 R'' Li a 3 3 PPh 3 R' R'' 3 Si 3 AcH R 3, rt 3 - R' 3 3 R'' R H 2 Tf 3 R 3 or or Tf 2 /a 3 Cu(II) H 2 3 or PdL n Chemistry of azides: S. Bräse, C. Gil, K. Knepper, V. Zimmermann, Angew. Chem. Int. Ed. 2005, 44, 5188

9 Preparation of Acetylenes. Amblard, J. H. Cho, R.. Schinazi, Chem. Rev. 2009, 109, 4207 Chemistry of alkynes:. Diederich, P. Stang, R. R. Tykwinski, Acetylene Chemistry. Chemistry, Biology, and Material Science, Wiley-VCH: Weinheim, 2004

10 CuAAC Regioselectivity 1,4 (anti) 1,5 (syn) R 1 + R 2 R 2 temp. R Cu(I) R 1 + R 2 R 2 R 1 J. D. Moses, A. D. Moorhouse, Chem. Soc. Rev. 2007, 36, 1249 V. D. Bock, H. Hiemstra, J. H. van Maarseveen, Eur. J. rg. Chem. 2006, 51

11 CuAAC chanism. Himo, T. Lovell, R. Hilgraf, V. V. Rostovtsev, L. oodleman, K. B. Sharpless, V. V. okin, J. Am. Chem. Soc. 2005, 127, 210

12 CuAAC chanism. Himo, T. Lovell, R. Hilgraf, V. V. Rostovtsev, L. oodleman, K. B. Sharpless, V. V. okin, J. Am. Chem. Soc. 2005, 127, 210

13 CuAAC chanism V. D. Bock, H. Hiemstra, J. H. van Maarseveen, Eur. J. rg. Chem. 2006, 51

14 CuAAC CuAAC with copper salts generated in situ from Cu(II) It appears to be the only three-atom dipole which is nearly devoid of side reactions % CuS4 + ascorbic acid or sodium ascorbate, variety of solvents including water, ph 4-12, rt, 6 to 36 h; or water t-buh, Cu metal, stirring for 24h at rt copper(i) salts can be used directly, but they require C as co-solvent and 1eq of nitrogen base (2,6-lutidine, DIPEA etc.) but side products can be formed: bisacetylenes, bis(triazoles) and 5-hydoxytriazoles; better results without oxygen - TBTA is to avoid this problem V. V. Rostovtsev, L. G. Green, V. V. okin, K. B. Sharpless, Angew. Chem. Int. Ed. 2002, 41, 2596 or a comprehensive list of Cu(I) sources, see: M. ldal, C. W. Tornøe, Chem. Rev. 2008, 108, 2952

15 CuAAC Synthesis of new nitrogen tetradentate ligands for Cu(I) catalyzed reaction Ph + 3 Ph 1 mol% [Cu(C) 4 ]P 6 1 mol% Ligand 2:1 tert-buh:h 2 RT, 24h, air Ph Ph Ph none Ph H, Ph Ph TBTA 1 % > 95 % 84 % Ph T. R. Chan, R. Hilgraf, K. B. Sharpless, V. V. okin, rg. Lett. 2004, 6, 2853

16 CuAAC Synthesis of new nitrogen tetradentate ligands for Cu(I) catalyzed reaction n = 1, 2 ( ) n Br R + a mol% CuI 2 mol% L C/H 2 1:1 RT, 10h R Ph R = 4-i-Pr, 4-t-Bu, 2-, 2,4-2, 2,3,4,5,6-5, 2,6-2, 2-C 3 2-pyridyl, phenethyl, 2-(1-ethylbenzimidazolyl)methyl. Li, T. S. A. Hor, Chem. Eur. J. 2009, 15, 10585

17 CuAAC Use of HC ligands for Cu(I) catalyzed reaction Cu Cu X X (Is)CuX (SIs)CuX S. Diez-Gonzalez, A. Correa, L. Cavallo, S. P. olan, Chem. Eur. J. 2006, 12, 7558

18 CuAAC Use of bidentate S, ligands for Cu(I) catalyzed reaction 2 S Cu reactions proceeds with 1 mol% of cat. in C at RT under air, no additional base needed synthesis of polysaccharide dendrimers via coupling of glucosyl azides with phenyl-propargyl ethers P. abbrizzi, S. Cicchi, A. Brandi, E. Sperotto, G. van Koten, Eur. J. rg. Chem. 2009, 5423

19 CuAAC [Cu(PPh 3 ) 3 ]Br and [(Et) 3 PCu]I catalysts soluble in organic solvents Ac Ac Ac Ac + Ac Ac Ac Ac eq [Cu(PPh 3 ) 3 ]Br or [(Et) 3 PCu]I 3 eq DIPEA rt or MW Ac Ac Ac Ac Ac Ac Ac Ac also dendritic structures. Perez-Balderas, M. rtega-munoz, J. Morales-Sanfruto,. Hernandez-Mateo,. G. Calvo-lores, J. A. Calvo-Asin, J. Isac-Garcia,. Santoyo-Gonzalez, rg. Lett. 2003, 5, 1951 P. Wu, A. K. eldman, A. K. ugent, C. J. Hawker, A. Scheel, B. Voit, J. Pyun, J. M. J. rechet, K. B. Sharpless, V. V. okin, Angew. Chem. Int. Ed. 2004, 43, 3928

20 CuAAC A tandem one-pot diazo transfer - click reaction using heterogenous copper catalyst CuC contains Cu 2 and Cu on charcoal commercially available recyclable copper does not leak into the solution C.-T. Lee, S. Huang, B. H. Lipshutz, Adv. Synth. Cat. 2009, 351, 3139 Azide transfer: P. B. Alper, S.-C. Hung, C.-H. Wong, Tetrahedron Lett. 1996, 37, 6029 J. T. Lundquist, J. C. Pelletier, rg. Lett. 2001, 3, 781 W. S. Horne, C. S. Stout, M. R. Ghadiri, J. Am. Chem. Soc. 2003, 125, 9372

21 CuAAC A tandem one-pot diazo transfer - click reaction using heterogenous copper catalyst C.-T. Lee, S. Huang, B. H. Lipshutz, Adv. Synth. Cat. 2009, 351, 3139 Azide transfer: P. B. Alper, S.-C. Hung, C.-H. Wong, Tetrahedron Lett. 1996, 37, 6029 J. T. Lundquist, J. C. Pelletier, rg. Lett. 2001, 3, 781 W. S. Horne, C. S. Stout, M. R. Ghadiri, J. Am. Chem. Soc. 2003, 125, 9372

22 CuAAC Click reactions catalyzed by Cu 2 /Cu nanoparticles Reaction strongly accelerated by addition of Et 3 I. S. Park, M. S. Kwon, Y. Kim, J. S. Lee, J. Park, rg. Lett. 2008, 10, 497 ther examples of use of nanoparticles: J. Y. Kim, J. C. Park, H. Kang, H. Song, K. H. Park, Chem. Commun. 2010, 439 L. D. Pachon, J. Maarseveen, G. Rothenberg, Adv. Synth. Catal. 2005, 347, 811 M. L. Kantama, V. S. Jayaa, B. Sreedhara, M. M. Raoa, B. M. Choudaryb, J. Mol. Catal. A: Chem. 2006, 256, 273 G. Molteni, C. L. Bianchi, G. Marinoni,. Santo and A. Ponti, ew J. Chem. 2006, 30, 1137

23 CuAAC - examples Radioisotope labeling imaging probes for Positron Emission Tomography Ac Tf Ac Ac 3 K 18 K 2 C 3, KH 2 P 4 C, 85 C 2.5 min Ac Ac Ac 3 18 ah 5 min, 60 C H H H 3 18 t 1/2 = 109 min H peptide H H H H 2 H peptide H 2 H H H H D -Phe g Gly Asp [ 18 ]Glc-RGD α ν β 3 integrin-binding peptide 20 % total yield, 70 min S. Maschauer, J. Einsiedel, R. Haubner, C. Hocke, M. cker, H. H., T. Kuwert, P. Gmeiner,. Prante, Angew. Chem. Int. Ed. 2010, 49, 976 T. Ramenda, T. Kniess, R. Bergmann, J. Steinbach,. Wuest, Chem. Commun. 2009, 7521

24 CuAAC - examples A click reaction used to obtain a highly functional ligand for a transition metal complex R Cu(I) R

25 CuAAC - examples A click reaction used to obtain a highly functional ligand for a transition metal complex R Cu(I) R [Ir(ppy) 2 (pytl-βcd)]cl (Φ=0.54, τ=2800 ns) M. elici, P. Contreras-Carballada, Y. Vida, J. M. M. Smits, R. J. M. olte, L. De Cola, R. M. Williams, M. C. eiters Chem. Eur. J. 2009, 15, M. bata, A. Kitamura, A. Mori, C. Kameyama, J. A. Czaplewska, R. Tanaka, I. Kinoshita, T. Kusumoto, H. Hashimoto, M. Harada, Y. Mikata, T. unabiki, S. Yano, Dalton Trans. 2008, 3292 D. J. V. C. van Steenis,. R. P. David, G. P.. van Strijdonck, J. H. van Maarseveen, J.. H. Reek, Chem. Commun. 2005, 4333

26 CuAAC - examples Synthesis of a rotaxane templated by a click reaction R 3 + R 1) 0.2 eq Cu(C) 4 P eq Py ClCH 2 CH 2 Cl 2) KC Cu+ R Cu + R R R R = 82 % V. Aucagne, K. D. H., D. A. Leigh, P. J. Lusby, D. B. Walker, J. Am. Chem. Soc. 2006, 128, 2186 or other examples, see: H. Zheng, W. Zhou, J. Lv, X. Yin, Y. Li, H. Liu, Y. Li, Chem. Eur. J. 2009, 15, 13253, and ref. therein

27 CuAAC - examples Molecular electronics - single molecular junction closed using click chemistry M. Mayor, Angew. Chem. Int. Ed. 2009, 48, 5583

28 CuAAC - examples DA modification labeling, branching, cyclization etc. Ph Ph Ph TBTA - Cu(I)-stabilising ligand. Amblard, J. H. Cho, R.. Schinazi, Chem. Rev. 2009, 109, 4207 P. M. E. Gramlich, C. T. Wirges, A. Manetto, T. Carell, Angew. Chem. Int. Ed. 2008, 47, 8350 T. R. Chan, R. Hilgraf, K. B. Sharpless, V. V. okin, rg. Lett. 2004, 6, 2853

29 CuAAC - examples Analysis of DA sequence H H L = fluorescent H THPTA E. Jentzsch, A. Mokhir, Inorg. Chem. 2009, 48, 9593

30 CuAAC with Porphyrins 2 H 2 i Cu( 3 ) 2 3H 2. Ac 2 CH 2 Cl 2, RT i Sn/HCl CHCl C i = Ph, 4-C 6 H 4, 4-C 6 H 4,4-ClC 6 H 4 3 1) a 2, H 2 S 4 TH/H 2, RT 2) a 3 i D.-M. Shen, C. Liu, Q.-Y. Chen, Eur. J. rg. Chem. 2007, 1419

31 CuAAC with Porphyrins 0.1eq CuI or CuCl DM, RT complex mixtures 3 PPh 3 i 0.1eq CuBr(PPh 3 ) 3 DM, RT i 98 % + Ph 0.1 eq CuS 4 5H eq ascorbic acid DM RT, 24h or 50 C, 3h. i Ph 92 % D.-M. Shen, C. Liu, Q.-Y. Chen, Eur. J. rg. Chem. 2007, 1419

32 CuAAC with Porphyrins 3 i + Ph. CuS 4 5H 2 ascorbic acid DM, 50 C i Ph i Ph i 98 % Ph D.-M. Shen, C. Liu, Q.-Y. Chen, Eur. J. rg. Chem. 2007, 1419

33 CuAAC with Porphyrins Coupling of azido-porphyrins with acetylene-substituted porphyrins M. Séverac, L. Le Pleux, L. A. Scarpaci, E. Blart,. dobel, Tetrahedron Lett. 2007, 48, 6518

34 CuAAC with Porphyrins Coupling of azido-porphyrins with acetylene-substituted porphyrins (a) Et 2 -B 3, CH 2 Cl 2, 12 h, rt then DDQ, 1 h, rt (11%); (b) SnCl 2, HCl, CHCl 3, AcH, reflux, 12 h (76%); (c) a 2, a 3, TA, H 2, 0 C (95%); (d) Zn(Ac) 2, CH 2 Cl 2, H, 60 C, 2 h (100%) M. Séverac, L. Le Pleux, L. A. Scarpaci, E. Blart,. dobel, Tetrahedron Lett. 2007, 48, 6518

35 CuAAC with Porphyrins Coupling of azido-porphyrins with acetylene-substituted porphyrins (a) PhLi, TH, -78 C, H 2, DDQ (85%); (b) Zn(Ac) 2, CH 2 Cl 2, H, 60 C, 2 h (100%); (c) I 2, Ag 2, CH 3 C CH 2 Cl 2, 0 C, 1 h (73%); (d) HCl, CH 2 Cl 2 (100%); (e) i(ac) 2, DM, 110 C, 2 h (97%); (f) Pd/C, abh 4, CH 2 Cl 2, H, rt, 1 h (95%); (g) a 2, a 3, H 2 S 4, TH, H 2, rt, 1 h (85%) M. Séverac, L. Le Pleux, L. A. Scarpaci, E. Blart,. dobel, Tetrahedron Lett. 2007, 48, 6518

36 CuAAC with Porphyrins Coupling of azido-porphyrins with acetylene-substituted porphyrins M. Séverac, L. Le Pleux, L. A. Scarpaci, E. Blart,. dobel, Tetrahedron Lett. 2007, 48, 6518

37 CuAAC with Porphyrins Coupling of azido-porphyrins with acetylene-substituted porphyrins Side product from Staudinger reaction with PPh 3 M. Séverac, L. Le Pleux, L. A. Scarpaci, E. Blart,. dobel, Tetrahedron Lett. 2007, 48, 6518

38 CuAAC with Porphyrins Coupling of azido-porphyrins with acetylene-substituted porphyrins 18 % 41 % CuS 4-4H 2, ascorbic acid, DM, 50 C, 50h M. Séverac, L. Le Pleux, L. A. Scarpaci, E. Blart,. dobel, Tetrahedron Lett. 2007, 48, 6518

39 CuAAC with Porphyrins Coupling of azido-porphyrins with acetylene-substituted porphyrins H H Ts H H S + H H. B 3 Et 2 DDQ CH 2 Cl 2 H S S H ah DABC TH, RT H S S H S S. Punidha, J. Sinha, A. Kumar, M. Ravikanth, J. rg. Chem. 2008, 73, 323

40 CuAAC with Porphyrins Coupling of azido-porphyrins with acetylene-substituted porphyrins H (CH2 ) 3 Br (CH2 ) 3 3 H H H H 20 eq Br(CH 2 ) 3 Br K 2 C 3 DM, RT H H H H a 3 acetone rfl H H H H S. Punidha, J. Sinha, A. Kumar, M. Ravikanth, J. rg. Chem. 2008, 73, 323

41 CuAAC with Porphyrins (CH2 ) 3 3 H H H H + H S H 0.1 CuS 4 5H sodium ascorbate acetone/h 2 1:1 80 C, 4d S H H H H H S H 46 % S S. Punidha, J. Sinha, A. Kumar, M. Ravikanth, J. rg. Chem. 2008, 73, 323

42 CuAAC with Porphyrins 0.1 eq CuI 1.0 eq DIPEA V. S. Shetti, M. Ravikanth, Eur. J. rg. Chem. 2010, 494

43 CuAAC with Porphyrins Coupling of azido-porphyrins with SWTs T. Palacin, H. Le Khanh, B. Jousselme, P. Jegou, A. iloramo, C. Ehli, D. M. Guldi, S. Campidelli, J. Am. Chem. Soc. 2009, 131, 15394

44 CuAAC with Porphyrins Coupling of azido-porphyrins with SWTs H H Click reaction conditions: 0.7 eq Cu(C) 4 P 6 40 eq 2,6-lutidine THPTA a spatula tip deoxygenated, MP, rt, 48h atmosphere H THPTA T. Palacin, H. Le Khanh, B. Jousselme, P. Jegou, A. iloramo, C. Ehli, D. M. Guldi, S. Campidelli, J. Am. Chem. Soc. 2009, 131, 15394

45 CuAAC with Porphyrins Coupling of azido-porphyrins with SWTs a) Cu(C) 4 P 6, 2,6-lutidine, THPTA, TH/H 2, 50, 48%; b) a 3, TH/H 2, 60, 85%; c) SWTs 6, Cu(C) 4 P 6,,6-lutidine, THPTA, MP, rt T. Palacin, H. Le Khanh, B. Jousselme, P. Jegou, A. iloramo, C. Ehli, D. M. Guldi, S. Campidelli, J. Am. Chem. Soc. 2009, 131, 15394

46 CuAAC with Porphyrins Glycoporphyrins by microwave-assisted click reactions 0.3 eq CuCl. B. Locos, C. C. Heindl, iadna Corral, M.. Senge, E. M. Scanlan, Eur. J. rg. Chem (ASAP)

47 CuAAC with Porphyrins -fused porphyrin with an oligoarginine side chain Ph Ph H Ph -fused porphyrin Ph 1 eq CuI i-pr 2 Et CH 2 Cl 2 Ph H Ph Ph Ph TA m-cresole thioanisole [g(pbf)] 9 H + (g) 9 H 2 3 [g(pbf)] 9 H Ph H 2 S H - + H 3 Ph H Ph g(pfb) Ph Y. Ikawa, H. Harada, M. Toganoh, H. uruta, Bioorg. d. Chem. Lett. 2009, 19, 2448

48 CuAAC with Porphyrins Porphyrin quinolone conjugates R H H H K 2 C 3 DMS C R H H Zn(Ac) 2 5H 2 CHCl 3 /H 2:1 50 C. R R R R Zn. CuS 4 5H 2 ascorbic acid DM, 50 C R Zn C 2 Et Et 3 C 2 Et Click reaction - for each alkyne group 1 eq CuS 4 5H 2 R Et R 2 eq ascorbic acid % 2 eq azidoquinolone. C. Santo, A. C. Cunha, M. C. B. V. de Souza, A. C. Tomé, M. G. P. M. S. eves, V.. erreira, J. A. S. Cavaleiro, Tetrahedron Lett. 2008, 49, 7268

49 Copper-free cycloaddition of azides and alkynes complexation of Cu by the products of click reactions, in particular porphyrins glycopolymers, glycodendrimers etc. permitted daily exposure (PDE) to copper at 50 μg/k for oral doses and 10 μg/kg for intravenously administered drugs (European dicines Agency) C. R. Becer, R. Hoogenboom, U. S. Schubert, Angew. Chem. Int. Ed. 2009, 48, 4900 J.. Lutz, Angew. Chem. Int. Ed. 2008, 47, 2182 A. Cano-dena, P. Vandezande, D. ournier, W. Van Camp,. E. Du Prez, I.. J. Vankelecom, Chem. Eur. J. 2010, 16, 1061 The European Agency for the Evaluation of dicinal Products, 2007

50 Copper-free cycloaddition of azides and alkynes Cycloaddition of azides to alkynes activated by electron withdrawing groups H Et 2 C H 3 3 H 2, 70 C, 1h + C 2 Et Et 2 C Et 2 C H H C 2 Et C 2 Et 96 % H. C. Kolb, M. G. inn, K. B. Sharpless, Angew. Chem. Int. Ed. 2001, 40, 2004 ther examples: C. W. Tornøe, C. Christensen, M. ldal, J. rg. Chem. 2002, 67, 3057 S. S. van Berkel, A. J. Dirks, S. A. euwissen, D. L. L. Pingen,. C. Boerman, P. Laverman,. L. van Delft, J. J. L. Cornelissen,. P. J. Rutjes, ChemBioChem 2008, 9, 1805

51 Copper-free cycloaddition of azides and alkynes Strain-promoted azide-alkyne cycloaddition (SPAAC) - with cyclooctyne derivatives C 2 H C 2 H H 2 C 1 st generation 2 nd generation 3 rd generation R' 3 + R'' rt R' R'' + R' R'' S. T. Laughlin, J. M. Baskin, S. L. Amacher, C. R. Bertozzi, Science 2008, 320, 664 J. A. Codelli, J. M. Baskin,. J. Agard, C. R. Bertozzi, J. Am. Chem. Soc. 2008, 130, E. M. Sletten, C. R. Bertozzi, rg. Lett. 2008, 10, 3097 J. A. Johnson, J. M. Baskin, C. R. Bertozzi, J.. Koberstein,. J. Turro, Chem. Commun. 2008, 3064

52 Copper-free cycloaddition of azides and alkynes Cycloaddition of azides with oxanorbornadiene derivatives X R'' X = C 3, C 2 R' H 2 or H or CHCl 3 rt R' X R'' - R' X R'' + regioisomer S. S. van Berkel, A. J. Dirks, M.. Debets,. L. van Delft, J. J. L. M. Cornelissen, R. J. M. olte,. P. J. T. Rutjes, ChemBioChem 2007, 8, 1504

53 Copper-free cycloaddition of azides and alkynes Cycloaddition of alkynes activated in other ways for example with ischer carbenes S. Sawoo, P. Dutta, A. Chakraborty, R. Mukhopadhyay,. Bouloussa, A. Sarkar, Chem. Commun. 2008, 5957

54 Copper-free cycloaddition of azides and alkynes Cycloaddition of azides with arynes. Shi, J. P. Waldo, Y. Chen, R. C. Larock, rg. Lett. 2008, 10, 2409 L. Campbell-Verduyn, P. H. Elsinga, L. Mirfeizi, R. A. Dierckx, B. L. eringa, rg. Biomol. Chem. 2008, 6, 3461

55 Copper-free cycloaddition of azides and alkynes Ruthenium catalyzed cycloaddition works also for terminal alkynes allows to completely control regioselectivity of reaction (1,4- or 1,5-) by changing the ligands possibility of further functionalization of triazole ring L. Zhang, X. Chen, P. Xue, H. H. Y. Sun, I. D. Williams, K. B. Sharpless, V. V. okin, G. Jia, J. Am. Chem. Soc. 2005, 127, B. C. Boren, S. arayan, L. K. Rasmussen, L. Zhang, H. Zhao, Z. Lin, G. Jia, V. V. okin, J. Am. Chem. Soc. 2008, 130, 8923 J. E. Hein, J. C. Tripp, L. B. Krasnova, K. B. Sharpless, V. V. okin, Angew. Chem. Int. Ed. 2009, 48, 8018

56 Thiol-Ene Click Reaction orthogonal to a wide range of functional groups compatible with water and oxygen stability of thioether linkage under acidic, basic and reducing conditions no heavy metals needed complete atom economy drawbacks: reversibility of thiyl radical addition under some donditins, formation of disulfide side products A. Dondoni, Angew. Chem. Int. Ed. 2008, 47, 8995 C. R. Becer, R. Hoogenboom, U. S. Schubert, Angew. Chem. Int. Ed. 2009, 48, 4900 D. Ramos, P. Rollin, W. Klaffke, J. rg. Chem. 2001, 66, 2948 S. Wittrock, T. Becker, H. Kunz, Angew. Chem. Int. Ed. 2007, 46, 5226

57 Thiol-Ene Click Reaction K. L. Killops, L. M. Campos, C. J. Hawker, J. Am. Chem. Soc. 2008, 130, 5062

58 ucleophilic Addition and Substitution with Thiols Michael addition PIPAM = poly(-isopropylacrylamide) M. Li, P. De, S. R. Gondi, B. S. Sumerlin, J. Polym. Sci. Part A 2008, 46, 5093

59 ucleophilic Addition and Substitution with Thiols omatic substitution of fluorine 40 C, 1h V. Ladmiral, G. Mantovani, G. J. Clarkson, S. Cauet, J. L. Irwin, D. M. Haddleton, J. Am. Chem. Soc. 2006, 128, 4823 S. G. Spain, M. I. Gibson,. R. Cameron, J. Polym. Sci. Part A 2007, 45, 2059 C. R. Becer, K. Babiuch, K. Pilz, S. Hornig, T. Heinze, M. Gottschaldt, U. S. Schubert, Macromolecules 2009, 42, 2387

60 Diels-Alder Click Reaction Preparation of polyphenylene dendrimers + -C G. ranc, A. K. Kakkar, Chem. Eur. J. 2009, 15, 5630

61 Diels-Alder Click Reaction Preparation of polyphenylene dendrimers G. ranc, A. K. Kakkar, Chem. Eur. J. 2009, 15, Morgenroth, E. Reuther, K. Müllen, Angew. Chem. Int. Ed. Engl. 1997, 36, 631 E. V. Andreitchenko, C. G. Clark, Jr., R. E. Bauer, G. Lieser, K. Müllen, Angew. Chem. Int. Ed. 2005, 44, 6348

62 Diels-Alder Click Reaction Preparation of star polymers A. Dag, H. Durmaz, G. Hizal, U. Tunca, J. Polym. Sci. Part A 2008, 46, 302

63 Diels-Alder Click Reaction RAT-HDA (Reversible Addition ragmentation chain-transfer - - Hetero-Diels-Alder) A. J. Inglis, S.Sinnwell, M. H. Stenzel, C. Barner-Kowollik, Angew. Chem. Int. Ed. 2009, 48, 2411

64 Summary Click reactions found numerous applications in all areas of chemical synthesis (>1000 papers in 2008), in spite of limited research on their methodology Click chemistry with porphyrins is sill a challange

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