2 Introduction Dudley 4-2- SES SES-Cl SES- 2 SES 2 Aldrichimica Acta ALDIC WELCMES TE 37T GLM T MILWAUKEE Acta Aldrichimica Acta 40 Aldrichimica Acta

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1 2007 VLUME 7 UMBE 3 保護化試薬 Protection Dudley Benzylation eagent Trichloroacetimidate eagents (2-Trimethylsilyl)- ethanesulfonyl eagents Ethynylnaphthalenes Fluorous Protecting Groups Common eagents for Protection Common eagents for Deprotection 2-Benzyloxy-1-methylpyridinium triflate: an air-stable pre-activated pyridinium salt for the mild benzylation of alcohols under neutral conditions. sigma-aldrich.com

2 2 Introduction Dudley 4-2- SES SES-Cl SES- 2 SES 2 Aldrichimica Acta ALDIC WELCMES TE 37T GLM T MILWAUKEE Acta Aldrichimica Acta 40 Aldrichimica Acta Lab otes 4 12 UL V L. 3 9, VEL PD C: EAGETS A EW GEEATI AD CATALYSTS F F AI-STABLE FACILITATIG PD CATALYSTS SYTESIS V L. 3 98, Enzymes in rganic Synthesis Modern Strategies in rganic Catalysis M Polymerization in Facilitated Synthesis Pd -eterocyclic Carbene Polyurea-Encapsulated (C) Catalysts for Cross-Coupling Palladium eactions Catalysts sigma-aldrich.com s i g m a - a l d r i c h. c o m / j a p a n Dudley 2-benzyloxy-1-methylpyridinium triflate Tel: Fax: [email protected]

3 Dudley Benzylation eagent Williamson Figure 1 triflic acid, Tf p TMS Gregory Dudley 1 Figure 2 Mg Scheme 1 Table 1 1,2- DCE BTF BTF methyl 3-hydroxy-2- methylpropionate entry 6 100% entry 7 eferences: (1) (a) Poon, K. W. C.; Dudley, G. B. J. rg. Chem. 2006, 71, (b) Poon, K. W. C. et al. Synlett 2005, Williamson ether synthesis Trichloroacetimidates Alkoxypyridinium sulfonate Ph X (strongly basic) Tf Bn C 3 CCl 3 Ph Tf (strongly acidic) Mg, solvent, C, 1 day C3 Tf Ph Bn Mg C 3 (neutral) Tf Figure 1 C3 Scheme 1 Entry Benzylation Product Solvent 1 M Yield (%) 1 DCE C (C2)3C2Bn benzene 93 3 toluene 91 4 BTF >95 5 Ph Bn BTF > TMS C 3 Bn BTF 85 3C 2C Bn BTF 100* Figure 2 Dudley Benzylation eagent 8 3C C3 C 3 Bn BTF 88 9 Bn BTF 80 *conversion Table 1 2-Benzyloxy-1-methylpyridinium triflate 8 C F 3 4 S FW: [ ] C 3 S CF G 1 g 15, G 5 g 50,000 Tel: Fax: [email protected]

4 4 Trichloroacetimidate eagents Trichloroacetimidate eagents 1 securinine 2 C PKC 3 Laurencin 4 Scheme 1 4- DDQ CA p- PMB Scheme 2 4- syn- anti- 5 Scheme 6,7 eferences: (1) Greene, T. W.; Wuts, P. G. M. Protective Groups in rganic Synthesis, 3rd ed.; John Wiley & Sons: ew York, (2) onda, T. et al. rg. Lett. 2004, 6, 87. Attempted allylation with allyl bromide under basic conditions did not provide the desired compound. (3) Goekjian, P. G. et al. J. rg. Chem. 1999, 64, (4) Krüger, J.; offmann,. W. J. Am. Chem. Soc. 1997, 119, Attempted allylation under basic conditions resulted in silyl migration. (5) Ichikawa, Y. et al. rg. Lett. 2006, 8, (6) Manaviazar, S. et al. rg. Lett. 2006, 8, (7) Keck, G. E. et al. rg. Lett. 2006, 8, Allyl 2,2,2-trichloroacetimidate, 96% 8 C 5 6 Cl 3 FW: [ ] CCl G 5 g 15,000 4-Methoxybenzyl-2,2,2-trichloroacetimidate 8 C Cl 3 2 FW: CCl 3 [ ] 3C G 5 g 10, G 25 g 39,600 Benzyl 2,2,2-trichloroacetimidate, 99% C 9 8 Cl 3 FW: [ ] CCl G 5 g 3, G 25 g 10,700 tert-butyl 2,2,2-trichloroacetimidate, 96% C 6 10 Cl 3 FW: [ ] C 3 3C 3C CCl G 1 g 3, G 5 g 9, G 25 g 21,100 TBS Boc C 2Et 3C 2C C C2Cl2, Tf, rt 76% F pet. ether, Tf2, rt 3C 3C C3 3C 91% C2Et Et2, Tf, rt 85% BPS BPS Boc C 6 12, Tf, rt 89% TBS CCl3 2 Cl 3C C2 2 Cl 3C 3C C 2Et 3C2C or C2Cl2, PPTS, rt 77% C2Cl2, CSA, rt 76% CCl 3 PMB CCl3 C3 F 3C securinine Br 2 Cl 3C C2 2 Cl C2Et Ac laurencin 3C 3C C3 3C PMB PMB BPS Scheme 1 PMB C3 Scheme 2 BPS Scheme 3 Monthly Chemistry E-ewsletter Got Chemews? sigma-aldrich.com/chemnews s i g m a - a l d r i c h. c o m / j a p a n Tel: Fax: [email protected]

5 (2-Trimethylsilyl)- ethanesulfonyl eagents 1986 Weinreb 2- SES Figure 1 SES 2 SES-Cl Boc- Fmoc- Z- Boger D- L- SES- Cl Scheme 1 Boger amoplanin 3 Chlorofusin 4 0 1,4- SES SES Scheme SES- 2 Bolm Mancheño SES- 2 Scheme 6 Lamaty aza-baylis-illman SES- 2 SES - - 2,3- Scheme 4 7 SES- 2 8,9 Scheme 5 eferences: 1) Weinreb, S. M.; albovsky, J. L. b-trimethylsilylethanesulfonyl Chloride, in Encyclopedia of eagents for rganic Synthesis; Paquette, L. A., Ed.; Wiley: Chichester, U.K., 1995, Vol. 7, p (2) ibière, P. et al. Chem. ev. 2006, 106, (3) (a) ew, Y. et al. J. Am. Chem. Soc. 2004, 126, (b) Jiang, W. et al. J. Am. Chem. Soc. 2003, 125, (c) Jiang, W. et al. J. Am. Chem. Soc. 2002, 124, (4) Desai, P. et al. rg. Lett. 2003, 5, (5) hno,. et al. J. Am. Chem. Soc. 2004, 126, (6) Mancheño,. G.; Bolm, C. rg. Lett. 2006, 8, (7) Declerck, V. et al. J. rg. Chem. 2004, 69, (8) Masllorens, J. et al. Tetrahedron 2005, 61, (9) Parker, L. L. et al. Tetrahedron 2003, 59, Bn 2 2 Br SES 2 Br 3C Si 3C C3 SES S 1) TMSCl, 55 C, 2 h SES Boc Boc 2) SES-Cl, Et3 55 C, 13 h SESCl, Et 3 DMF, 0 C CsF, DMF 95 C, 12 h S C C SES Boc Br Bn SES Bn Br 5 mol % Fe(acac)3 SES- 2, PhI= (Boc) 2 SES Boc C3C, rt, 18 h C 3 Boc SES Me 0.5 eq DABC i-pr, 70 C SES 2 C 3 Bn SES SES S C3 Br SES C2 Figure 1 Scheme 1 SES n n n n n 2 2 Me Scheme 2 Scheme 3 C 3 Scheme 4 5 (2-Trimethylsilyl)- ethanesulfonyl eagents n 2-(Trimethylsilyl)ethanesulfonyl chloride 8 C 5 13 Cl 2 SSi S FW: C Si Cl [ ] 3C C G 1 g 17, G 5 g 60,000 ', ' =, Ts n n = 1-4 n Scheme 5 2-(Trimethylsilyl)ethanesulfonamide 8 C SSi FW: C S Si 2 [ ] 3C C G 1 g 19,100 Tel: Fax: [email protected]

6 6 Ethynylnaphthalenes Ethynylnaphthalenes David Crich s naphthyl -2-propynyl ether bromo-1-propynyl naphthalene DDQ 2-3 Scheme naphthyl -2-propyn-1-ol 3-1-naphthyl -2-propyn-1-ol dimethyl acetylenedicarboxylate Scheme 2 3 eferences: (1) (a) Crich, D.; Jayalath, P. rg. Lett. 2005, 7, (b) Crich, D. et al. J. rg. Chem. 2006, 71, (2) Crich, D.; Wu, B. rg. Lett. 2006, 8, (3) Tanaka, K. et al. rg. Lett. 2005, 7, Et2C Et 2C 3C C3 C 2Et C2Et C 3 C 3 + a DDQ Br C 2Cl 2/ 2, 2-3 h 5 mol % [h(cod)2]bf4 5 mol % (S)-8-BIAP 3C C3 Et2C C 3 C 3 Et 2C C2Cl2, rt, 16 h * Scheme 1 C2Et C2Et 75%, 96% ee Scheme 2 1-(-Bromo-1-propynyl)naphthalene 8 C 13 9 Br FW: [ ] Br G 1 g 14,100 -(1-aphthyl)-2-propyn-1-ol 8 C FW: [ ] G 1 g 12, G 5 g 44,600 2,4,6-Trimethylbenzoyl chloride 2,4,6- LiAl 4 C 3 3 C Cl C 3 pyridine, CCl 3 0 C, 14h - 23 C, 1h 3 C C 3 LiAl 4 C 3 Et 2, 20 C, 2h s i g m a - a l d r i c h. c o m / j a p a n 2,4,6-Trimethylbenzoyl chloride C Cl FW: [ ] C G 1 g 8, G 5 g 30,100 eferences: (1) (a) Corey, E. J. et al. J. Am. Chem. Soc. 1969, 91, (b) Bolton, I. J. et al. J. Chem. Soc. C 1971, (2) Greene, T. W.; Wuts, P. G. M. In Protective Groups in rganic Synthesis, 3rd ed.; John Wiley & Sons: ew York, 1999; p C Cl C3 Tel: Fax: [email protected]

7 Fluorous Protecting Groups 1 heavy fluorous products fluorous solid-phase extraction, F-SPE light fluorous compounds 2,3 F-Boc- F-Boc- 2- tert-butoxycarbonyloxyimino - 2-phenylacetonitrile Boc- F-Boc- F-Boc FluoroFlash DA - F-Boc- Scheme 1 5 F-PMB- F-PMB- p- PMB- F-PMB F-PMB PMB 3,4- DMB F-PMB PMB Scheme 2 6 F-Trityl Alcohol and Chlorides Sigma-Aldrich F-Trt, F-MMT, F-DMT F-Trt < F-MMT < F-DMT F-DMT F-SPE 7 F-Silanes F- TIPS 8,9 F- in situ F- F-Benzyl Alcohol, F-Fmoc-Cl, F-Z-Su 2 2 TP F-Boc- C 3 C3 C3 C 3 PMB 2 C 3 C3 C3 C3 C3 TFA C 2Cl 2 C 3 C 3 C3 F PMB PMB TP C 3 C 3 C 3 C8F17 F-Boc 3 + C 3 C3 C3 DMB F PMB DDQ 69% C3 C3 Scheme 1 Scheme 2 Discover Sigma-Aldrich s ewest Web-Based Seminar Fluorous Chemistry for Synthesis, Separation, and Enrichment Featuring the latest innovative chemical synthesis technologies and products Access directly via your desktop browser Convenient navigation Contents: Introduction Fluorous Separation Techniques Small Molecule Synthesis and Purification Fluorous ligonucleotide, Peptide, and Carbohydrate Chemistry Fluorous Products Available Through Sigma-Aldrich To view Sigma-Aldrich s Web-based chemistry seminar series, please visit sigma-aldrich.com/cheminars. 7 Fluorous Protecting Groups Tel: Fax: [email protected]

8 F-Protecting Groups 2-[(4,4,5,5,6,6,7,7,7-onafluoro-1,1-dimethylheptyloxy) carbonyloxyimino]-2-phenylacetonitrile, ; 97.0% C F FW: C (CF 2) 3CF G-F 1 g 13,300 2-[(4,4,5,5,6,6,7,7,8,8,9,9,9-Tridecafluoro-1,1-dimethyl nonyloxy)carbonyloxyimino]-2-phenylacetonitrile, ; 97.0% 1-(4-Methoxyphenyl)-1-[4-(1,1,2,2-8 perfluorodecyl)phenyl]-1-phenylmethyl chloride C ClF 17 FW: [ ] F 3C(F 2C) 7 Cl C G 1 g 19,800 Fluorous Protecting Groups C F FW: C (CF 2) 5CF G-F 1 g 13, G-F 5 g 55,000 2-[(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-eptadecafluoro- 1,1-dimethylundecyloxy)carbonyloxyimino]-2- phenylacetonitrile, ; 97.0% C F FW: [ ] C (CF 2) 7CF G-F 1 g 11, G-F 5 g 45,700 4-(4,4,5,5,6,6,7,7,7-onafluoroheptyloxy)benzyl alcohol, ; 97.0% C F 9 2 FW: F3C(F2C) G-F 1 g 17,000 4-(4,4,5,5,6,6,7,7,8,8,9,9,9-Tridecafluorononyloxy) benzyl alcohol, ; 97.0% C F 13 2 FW: F 3C(F 2C) G-F 1 g 22, G-F 5 g 89,600 4-(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11- eptadecafluoroundecyloxy)benzyl alcohol, ; 97.0% C F 17 2 FW: F3C(F2C) G-F 1 g 13, G-F 5 g 53,300 1-[4-(1,1,2,2-Perfluorodecyl)phenyl)-1,1-8 diphenylmethanol, 98% C F 17 FW: [ ] F 3C(F 2C) G 1 g 15,600 1,1-Di-(4-methoxyphenyl)-1-8 [4-(1,1,2,2-perfluorodecyl)phenyl]methanol, 97% C F 17 3 C 3 FW: [ ] F 3C(F 2C) 7 C G 1 g 14,400 Diisopropyl(3,3,4,4,5,5,6,6,6-nonafluorohexyl)silane, ; 95% C F 9 Si FW: C C 3 Si [ ] F 3C(F 2C) 3 3C C G-F 1 g 15,300 Diisopropyl(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl) silane, ; 95% C F 13 Si 3C C3 FW: Si [ ] F3C(F2C)5 3C C G-F 1 g 14, G-F 5 g 55,900 Diisopropyl(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadeca fluorodecyl)silane, ; 95% C F 17 Si FW: Si [ ] F 3C(F 2C) 7 3C C 3 3C C G-F 1 g 11, G-F 5 g 46,200 4-(3,3,4,4,5,5,6,6,6-onafluorohexyl)benzyl alcohol, ; 95% C F 9 FW: F3C(F2C) G-F 1 g 17,000 4-(3,3,4,4,5,5,6,6,7,7,8,8,8-Tridecafluorooctyl)benzyl alcohol, ; 97.0% C F 13 FW: F3C(F2C)5 [ ] G-F 1 g 17, G-F 5 g 72,000 s i g m a - a l d r i c h. c o m / j a p a n Tel: Fax: [email protected]

9 4-(,,4,4,5,5,6,6,7,7,,,9,9,10,10,10-eptadecafluorodecyl) benzyl alcohol, ; 9.0% C F 17 FW: [ ] F 3C(F 2C) G-F 1 g 13, G-F 5 g 53,600 2,7-Bis(1,1,2,2-perfluorooctyl)-9-8 fluorenylmethoxycarbonyl chloride, 9% C ClF 26 2 F (CF FW: C(F 2C) 5 2) 5CF G 1 g 25,200 -[4-(,,4,4,5,5,6,6,6-onafluorohexyl)benzyl oxycarbonyloxy]succinimide, ; 95.0% C F 9 5 FW: F3C(F2C)3 Cl G-F 1 g 23,100 -[4-(,,4,4,5,5,6,6,7,7,,,-Tridecafluorooctyl)benzyl oxycarbonyloxy] succinimide, ; 97.0% C F 13 5 FW: [ ] F3C(F2C) G-F 1 g 19, G-F 5 g 79,200 -[4-(,,4,4,5,5,6,6,7,7,,,9,9,10,10,10-eptadecafluorodecyl) benzyloxycarbonyloxy]succinimide, ; 97.0% C F 17 5 FW: [ ] F3C(F2C) G-F 1 g 20, G-F 5 g 81,000 9 Fluorous Protecting Groups oveyda-snapper Catalyst For Desymmetrization f meso-diols Marc Snapper Amir oveyda meso-1,2-1 88% mol % 3 C TBSCl, DIPEA 1 C 3 TBS TBS up to 96%, up to 96% ee (S)--[()-,-Dimethyl-2-butyl]-,-dimethyl-2- [(1-methyl-1-imidazol-2-yl)methylamino]butanamide C FW: C C G 1 g 18,000 eference: (1) Zhao, Y. et al. ature 2006, 443, 67. Tel: Fax: [email protected]

10 10 Fluorous Protecting Groups Fluorous Separation Media F-SPE light fluorous tag 10 FluoroFlash FluoroFlash SPE Figure 1 F-SPE eferences: (1) The fluorous products featured here are manufactured by Fluorous Technologies, Inc. U.S. patents 6,156,896; 5,859,247; 5,777,121 and 6,673,539 may protect use of these compounds. (2) Zhang, Q. et al. J. Am. Chem. Soc. 2004, 126, 36. (3) Curran, D. P.; deraotoshi, Y. Tetrahedron 2001, 57, (4) Curran, D. P. Synlett 2001, (5) Mamidyala, S. K.; Firestine, S. M. Tet. Lett. 2006, 47, (6) Curran, D. P.; Furukawa, T. rg. Lett. 2002, 4, (7) Pearson, W.. et al. J. rg. Chem. 2005, 70, (8) Palmacci, E.. et al. Angew. Chem. Int. Ed. 2001, 40, (9) Zhang, W. et al. J. Am. Chem. Soc. 2002, 124, (10) Zhang, W.; Curran, D.P. Tetrahedron 2006, 62, FluoroFlash is a registered trademark of Fluorous Technologies, Inc. Figure 1 Fluorous Separation Media FluoroFlash SPE Cartridges, 2 grams, cc tube, particle size 40µm EA-F 67,000 FluoroFlash SPE Cartridges, 5 grams, 10 cc tube, particle size 40µm EA-F 75,000 FluoroFlash SPE Cartridges, 10 grams, 60 cc tube, particle size 40µm EA-F 75,000 FluoroFlash SPE Cartridges, 20 grams, 60 cc tube, particle size 40µm EA-F 88,600 FluoroFlash SPE Cartridges, 20 grams, 60 cc tube, particle size 40µm EA-F 121,800 FluoroFlash TLC Plates, with F254 indicator EA-F 30,000 FluoroFlash Silica Gel 40 µm, particle size ~40µm EA-F 89,400 Lipshutz DCAD Coupling eagent s i g m a - a l d r i c h. c o m / j a p a n DEAD DIAD Bruce Lipshutz 1 DCAD DEAD DIAD DCAD DEAD DEAD DCAD DCAD C 3 C2 C 3 + Bn azodicarboxylate hydrazine reagent byproduct + + Di-(4-chlorobenzyl) azodicarboxylate DCAD C Cl FW: Tel: Fax: [email protected] PPh3 C 2Cl 2, rt Cl =PPh G 1 g 4, G 10 g 19,900 eferences: (1) Lipshutz, B.. et al. rg. Lett. 2006, 8, C3 C 2Bn C3 DCAD: 92% DEAD: 94% DIAD: 89% Cl

11 Common eagents for Protection 11 TMS Chlorotrimethylsilane, redistillation, ; 99% TMSCl C 3 9 ClSi FW: [ ] ML 100 ml 7, L 1 L 50,300 Bromotrimethylsilane, 97% TMSBr C 3 9 BrSi FW: [ ] G 5 g 2, G 25 g 7, G 100 g 16,300 Iodotrimethylsilane, 97% TMSI C 3 9 ISi FW: [ ] G 5 g 3, G 25 g 8, G 100 g 29,000 Trimethylsilyl trifluoromethanesulfonate, 99% TMS(Tf) C 4 9 F 3 3 SSi FW: [ ] G 10 g 6, G 50 g 18,200,-Bis(trimethylsilyl)acetamide, synthesis grade BSA C 8 21 Si 2 FW: [ ] ML 10 ml 1, ML 25 ml 3, ML 100 ml 8, L 1 L 67,200,-Bis(trimethylsilyl)trifluoroacetamide, ; 99% BSTFA C 8 18 F 3 Si 2 FW: [ ] G 5 g 4, G 25 g 15, G 100 g 53,800 -Methyl--(trimethylsilyl)trifluoroacetamide, derivatization grade MSTFA C 6 12 F 3 Si FW: [ ] ML 5 ml 5, X1ML 10 ml 7, ML 25 ml 15,700 TBDMS tert-butyldimethylsilyl chloride, reagent grade, 97% TBDMSCl C 6 15 ClSi FW: [ ] G 5 g 3, G 25 g 8, G 100 g 19, KG 1 kg 171, KG 10 kg 538,000 tert-butyldimethylsilyl trifluoromethanesulfonate, reagent grade, 98% TBDMS(Tf) C 7 15 F 3 3 SSi FW: [ ] G 1 g 3, G 5 g 6, G 25 g 20,200 -tert-butyldimethylsilyl--methyltrifluoroacetamide, > 97% MTBSTFA C 9 18 F 3 Si FW: [ ] ML 5 ml 20, X1ML 10 ml 26, ML 25 ml 36, ML 100 ml 139,600 TES Chlorotriethylsilane, 99% TESCl C 6 15 ClSi FW: [ ] G 5 g 3, G 25 g 12,800 TIPS Triisopropylsilyl chloride, 97% TIPSCl C 9 21 ClSi FW: [ ] G 10 g 9, G 50 g 27,200 Triisopropylsilyl trifluoromethanesulfonate, 97% TIPS(Tf) C F 3 3 SSi FW: [ ] G 10 g 10, G 50 g 28,700 Common eagents for Protection Tel: Fax: [email protected]

12 12 Common eagents for Protection TBDPS tert-butyl(chloro)diphenylsilane, 98% TBDPSCl C ClSi FW: [ ] G 2 g 2, G 10 g 6, G 50 g 22,000 DTBS Di-tert-butylsilyl bis(trifluoromethanesulfonate), 97% DTBS(Tf) 2 C F 6 6 S 2 Si FW: [ ] G 5 g 12, G 25 g 38,000 Boc Di-tert-butyl dicarbonate, reagent grade, 97% Boc anhydride C FW: [ ] G 25 g 2, G 100 g 9,000 Di-tert-butyl dicarbonate, eagentplus, 99% Boc anhydride C FW: [ ] G 10 g 2, G 50 g 9, G 100 g 16, KG 1 kg 94, KG 15 kg 744,000 2-(Boc-oxyimino)-2-phenylacetonitrile, 99% Boc- C FW: [ ] G 5 g 3, G 25 g 13, G 100 g 42,400 Fmoc Fmoc chloride, 97% Fmoc-Cl C Cl 2 FW: [ ] G 1 g 1, G 5 g 4, G 25 g 15,200 Z/Cbz Benzyl chloroformate, technical grade, 95% Z-Cl C 8 7 Cl 2 FW: [ ] G 5 g 1, G 100 g 5,200 Dibenzyl dicarbonate, 97% Z 2 C FW: [ ] G 1 g 3, G 5 g 10, G 25 g 36,300 Bn Benzyl chloride, eagentplus, 99% BnCl C 7 7 Cl FW: [ ] G 50 g 1, G 250 g 1, KG 1 kg 2, KG 2 kg 3, KG 4 kg 6,200 Bz Benzoyl chloride, eagentplus, 99% BzCl C 7 5 Cl FW: [ ] L 1 L 9,800 MEM 2-Methoxyethoxymethyl chloride, technical grade MEM-Cl C 4 9 Cl 2 FW: [ ] G 5 g 2, G 25 g 6,400 SEM 2-(Trimethylsilyl)ethoxymethyl chloride, technical grade SEM-Cl C 6 15 ClSi FW: [ ] G 1 g 4, G 5 g 14, G 25 g 53,000 s i g m a - a l d r i c h. c o m / j a p a n Tel: Fax: [email protected]

13 TMSE 2-(Trimethylsilyl)ethanol, 99% TMSE- C 5 14 Si FW: [ ] G 1 g 2, G 10 g 15, G 50 g 54,300 Ts p-toluenesulfonyl chloride, eagentplus, ; 99% TsCl C 7 7 Cl 2 S FW: [ ] G 5 g 1, G 100 g 2,200 Trt Trityl chloride, 9% Trt-Cl C Cl FW: [ ] T G 25 g 2,800 T G 100 g 5,600 T G 500 g 19,600 PMB 4-Methoxybenzyl bromide PMB-Br C 8 9 Br FW: [ ] G 5 g 6,100 TP,4-Dihydro-2-pyran, 97% C 5 8 FW: [ ] D ML 5 ml 1,900 D ML 100 ml 3,100 D ML 500 ml 12,200 EtG Ethylene glycol, eagentplus, ; 99% C FW: [ ] ML 500 ml 1, L 1 L 1, X500ML 3000 ml 5, L 4 L 6,200 1 Common eagents for Protection Potassium Cyclopropyltrifluoroborate ciprofloxacin Charette 1 Deng 2 1 BF 3 K Ar Br [Pd], base 1 Ar 2 2 Potassium cyclopropyltrifluoroborate C 3 5 BF 3 K FW: BF 3K G 1 g 10, G 5 g 43,200 (1) Charette, A. B. et al. Synlett 2005, 11, (2) Fang, G.-. et al. rg. Lett. 2004, 6, 357. Tel: Fax: [email protected]

14 14 Common eagents for Deprotection Common eagents for Deprotection Cesium fluoride, 99% CsF FW: [ ] G 25 g 8, G 100 g 18,300 Cesium fluoride, 99.9% CsF FW: [ ] G 5 g 4, G 25 g 10, G 100 g 22,700 ydrogen fluoride pyridine, hydrogen fluoride ~70%, pyridine ~30% F FW: [ ] G 25 g 5, G 100 g 14,400 Tetrabutylammonium fluoride hydrate, 98% C F x 2 FW: (anhydrous basis) [ ] G 10 g 9, G 100 g 55,100 Tetrabutylammonium fluoride solution, 1.0M tetrahydrofuran C F FW: [ ] ML 5 ml 2, ML 100 ml 8, ML 500 ml 16, L 2 L 51,000 Tetramethylammonium fluoride, 97% C 4 12 F FW: [ ] G 1 g 9, G 5 g 32,000 2,3-Dichloro-5,6-dicyano-p-benzoquinone, 98% C 8 Cl FW: 227 [ ] D G 5 g 3,300 D G 10 g 4,700 D G 100 g 32,600 Ammonium cerium(iv) nitrate, 99.99% 8 Ce 8 18 FW: [ ] G 50 g 8, G 250 g 23,400 Boron tribromide solution, 1.0M dichloromethane BBr 3 FW: [ ] ML 100 ml 12, ML 800 ml 63, L 2 L 143,000 Boron tribromide, eagentplus, ; 99% BBr 3 FW: [ ] G 100 g 11, G 500 g 31,400 p-toluenesulfonic acid monohydrate, eagentplus, 98.5% C S 2 FW: [ ] T G 5 g 1,300 T G 100 g 1,700 T G 500 g 2,300 s i g m a - a l d r i c h. c o m / j a p a n Ammonium cerium(iv) nitrate, ACS reagent, ; 98.5% 8 Ce 8 18 FW: [ ] G 50 g 2, G 250 g 6, G 500 g 10,300 Tel: Fax: [email protected]

15 ew Chiral Technologies from Sigma-Aldrich ChiroSolv TM Kits ChiroSolv , 6142, , 619, 6177 Web sigma-aldrich.com/chirosolv Chiral Phospholane Ligands 4+1 Web sigma-aldrich.com/ phospholane P P DuPhos P Fe P Ferrocenyl Phospholanes P BPE P Chiral phospholane ligands are sold in collaboration with Kanata Chemical Technologies Inc. for research purposes only. These compounds were made and sold under license from E. I. Du Pont de emours and Company, which license does not include the right to use the compounds in producing products for sale in the pharmaceutical field. MacMillan rganocatalysts TM Mac- MacMillan rganocatalyst antzsch 1 Mac- MacMillan TiPSY Catalysts MacMillan TiPSY Catalysts C 3 C 3 C 3 C 3 CF 3 C 2 Et 3 C C 3 Et SiPh 3 P SiPh SiPh 3 P SiPh sigma-aldrich.com

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