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1 - - Acros Organics 4 1,2 3 4 - - 4 5 [ 42643] TMS N,N- [15569] [19699] 6 [20195] pH 7 Acidic hydrolysis : Me3Si< Ph2 MeSi < Et3Si < tBuMe2Si < iPr3Si < tBuPh2 SiBasic hydrolysis :Me3Si ~ Ph2 MeSi < Et3Si < tBuMe2Si ~ tBuPh2Si < iPr3 SiAcros Organics AcroSeal AcroSeal Acros Organics [33784]NSiOOHONBHOOHSi[43024]HOOSi[42817 ][43869]BrOSi[33784][43024][42817][43869 ] 1.

2 Greene, T.; Wuts, P.; Protecting Groups in Organic Synthesis , 2nd Ed., Wiley, New York, Blau, K.; Halket, J.; Handbook of Derivatives for Chromatography , 2nd Ed., J. Wiley and Sons, New York, Chatgilialoglu, C.; Acc. Chem. Res., 1992, 25, Coats, R. M.; Denmark, S.; Handbook of Reagents for Organic Synthesis. Reagents, Auxillaries and Catalysts for C-C Bond Formation ; J. Wiley and Sons, GB, Kocienski; P. J.; Protecting Groups , 3rd Ed., Thieme: Stuttgart, Morita, T. et al.; Tetrahedron Lett., 1983, 21, Nelson, T. D.; Crouch, R. D.; Synthesis, 1996, AcroSeal GroupReagentCodeNotesMe3Si (TMS)Chlorotrimethylsilane42643 Used for the protection of alcohols, alkynes, amines and amino acids, carboxylic acids, phenols, ketones. Most easily cleaved of all silyl protecting groups in acid and , 1M solution in THF38161 Chlorotrimethylsilane, 1M solution in DCM38160Et3Si (TES)Chlorotriethylsilane, 1M solution in THF43325 Used for the protection of alcohols.

3 TES ethers can be selectively deprotected in the presence of TBDMS (TBDMS)tert-Butyldimethylsilyl chloride, in DCM36910 Used for the protection of alcohols, amines, thiols, lactams and carboxylic acids. Reaction with an alcohol requires a catalyst such as imidazole.[20094] is a convenient, ready-to-use DMF solution of TBDMSCl ( ) and imidazole ( ).tert-Butyldimethylsilyl chloride, 50 in PhMe43311 BDCS, silylation reagent20094tBuPh2Si (TBDPS)tert-Butylchlorodiphenylsilane430 92 Greater steric demand. Therefore, more stable than TBDMS to acid hydrolysis (>100x). Primary alcohols are protected in the presence of secondary for the protection of diols, diamines and GC Acros Organics Derivatisation ReagentCodeStructureNotesN,O-Bis(trimeth ylsilyl)acetamide15646 NOSiSiCommonly used derivatisation agents for acidic functional groups; , alcohols, enols, amines, amides, carboxylic acids, amino acids, phenols, steroids, biogenic amines, alkaloids, phosphites and , 10N,O-Bis(trimethylsilyl)trifluoroacetam ide 16800 NOSiFFFSiOne of the most potent silylation reagents used today.

4 It has two advantages over BSA in GC analysis: i) The by-products and the reagent itself are highly volatile so they cause minimal interference with the GC ) The presence of fluorine atoms results in less fouling of flame-ionisation detectors. [38932] contains 1% TMSCl, which increases the silylating power of the mixture for analytical ,O-Bis(trimethylsilyl)trifluoroacetamide , with 1% TMSCl38932N,O-Bis(trimethylsilyl)trifluo roacetamide, packaged in 1 ml ampoules32120N-Methyl-N-(trimethylsilyl) trifluoroacetamide (MSTFA)22158 NOSiFFFMSTFA and its by-product are even more volatile than BSTFA and its by-product. Used in the analysis of steroids11, fatty acids12 and nucleic acids by AcroSeal 43088 SiClClUsed for derivatisation of diols, diamines and hydroyxacids. 8. Toshima et al.; Tetrahedron Lett. 1989, 30, Barlos, K. et al.; J. Org. Chem., 1982, 47, Knapp, D. R.; Handbook of Analytical Derivatization Reactions John Wiley & Sons, New York, Donike, M.

5 ; Zimmermann, J.; J. Chromatogr., 1980, 202, Blum, W.; J. High Res. Chromatogr., Chromatogr. Commun., 1985, 718 & 1986, H Si-H [21292] [16482] [29106] 13 Acros Organics Silyl hydrideAcros Organics CodeCl3 SiH17460Et3 SiH21292Ph3 SiH16482Ph2 SiH232977 PhSiH329169 TMS3 SiH29106 PMHS(a)17509++++++++++++++++++++++++++++ (++++++++++++++++++(a) [CpRu(MeCN)3]PF[37789]14 [16481] - OTBDPS201 (87% yield):OTBDPSSi(OEt)33 OTBDPSSi(OEt)(EtO)3 SiH [16481][CpRu(MeCN)3]PF6[37789] 0 C to , 1 h, DCM 13. Burke, S. D.; Danheiser. R.; Handbook of Reagents for Organic Synthesis - Oxidising and Reducing Reagents John Wiley and Sons Ltd.)

6 , Trost, Barry M.; Ball, Zachary T. ; J. Am. Chem. Soc., 2005, 127, [20382] [42036] 17,18 [16481] 20,21,22 Hiyama C-C Stille (Sn) Kumada (Mg) Suzuki (B) Negishi (Zn) Acros Organics Hiyama 15 Mg Zn Sn RSiR'3 RSi-R'3F 16 SiOHRR1 RSiOOR1 ORRRPd(0) catalystFluoride source or basewhere R= normally Me or EtR1= Aryl, alkenyl, alkynyl, allyl, (alkyl)R2 = aryl, alkenyl, allyldialkylsilanolstrialkoxysilanesR2-X R2-R1 SiOMeOMeOMeR1R2X+3 mol % Pd(OAc)23 mol % IPrHCl2 eq. TBAF inTHF/dioxaneR1R2X= Cl, Bror {[(t-Bu)2P(OH)(t-Bu)2PO)]PdCl}2 TBAF, THF/MeCNOBzSiOEtOEtOEtR1+10 mol % Pd2(dba)TBAF, THFR1XR1X= Br, Ii) Mgii) Si(OR)4ori) Rh or Pd catalystii) (RO)3Si HSi(OR)3R1 15.

7 Hatanaka, Y.; Hiyama, T.; J. Org. Chem., 1988; 53, Denmark, S. E.; Regens, C. S.; Acc. Chem. Res., 2008, 41, Murata, Miki; Shimazaki, Ryuta; Watanabe, Shinji; Masuda, Yuzuru.; Synthesis, 2001, 15, Manoso, Amy S.; Ahn, Chuljin; Soheili, Arash; Handy, Christopher J.; Correia, Reuben; Seganish, W. Michael; DeShong, Philip; J. Org. Chem, 2004, 69, Manoso, Amy S.; DeShong, Philip; J. Org. Chem, 2001, 66, Lee, Hon Man; Nolan, Steven P.; Org. Lett., 2000, 2, Wolf, Christian; Lerebours, Rachel; Tanzini, Elizabeth H.; Synthesis, 2003, 13, Correia, Reuben; DeShong, Philip; J. Org. Chem, 2001, 66, Pd Hiyama 23 K2 PdCl4[19512] PEG-600[19224] 70 C 15 PEG [43306] [17461] 2 - [25051] Pd(OAc)2[19518] Pb Pd Pd Si(OR)3R2XR1orXR1X= Cl, Br, OTsR= Me, Et+K2 PdCl4 PEG-600 TBAF in THF, 70 CR1orR1R2R2 XRX= Br, IR= MeCO, MeO, Bn, Cl,Si(OR)3Pd(OAc)2, NaOH, waterheat or MWRY ields 70-98% - - [21646] [11331] Denmark Pd2(dba) [36934] C-2 Boc- 2 - Pb Nbocii) sat.

8 NaHCO3 NbocSiMeOHMe71%NMei) n-BuLi, Et2O, reflux, 5hNMeSiMeOHMe57%OSiOSiOSiii)NaH or NaOtBu /CuIPd2(dba) (5 mol %)tolueneNbocIRRNMeRYields 70-85%i) LDA, Me2 SiCl2, THF, 0 C, 18h 23. Srimani, Dipankar; Bej, Ansuman; Sarkar, Amitabha; J. Org. Chem, 2010, 75, Alacid, Emilio; Najera, Carmen; J. Org. Chem, 2008, 73, Denmark, Scott E.; Baird, John D.; Regens, Christopher S.; J. Org. Chem, 2008, 73, - - - - 26 neoliacinic 27 A [43618] TMSCH2 - [37746] Peterson TMSOTF[20944] 28 3- -1- [33904] 1,1- [10222] 79% SiMeMeMeSiMeMeMeESiMeMeMeSiMeMeMeEEE+BuL i+(- )stabili sed -cati onstabili sed -an ionEli mina ti onE+BrSiMeMeMei) M g[30 74 1]ii ) M e3 SiCl MgClSiMeMeMeMeTIPSOOHSiMeMeMeSiMeMeMeSiM eMeMeMeTIPSOOOR'MeOHOHHOOOHMeTESOTESOOTI PSMeOHHCeCl3, THF, -78oCPetersonEl imination[43 61 8]i) TIPS-C l [22 12 6][37 74 6]ii ) Si O2(A)

9 Tri cy cl ic core of neol iacini c aci dM eSiM eM eM eM eO E tE t OM eO E tM eO E tS iM e3 TMSOTfDCM, -75 C3hours++-s il yl cationElectrophili cadditionEli mination 26. Thomas, S. E.; Organic Synthesis. The Roles of Boron and Silicon. Oxford Uni. Press, Clark, J. S.; Baxter, C. A., Dossetter, A.; Poigny, S.; Castro, J. L.; Whittingham, W. G.; J. Org. Chem., 2008, 73, Polla, M; Frejd, T.; Acta Chemica Scandinavica, 1993, 47, ORGANICS CAS Allyl(chloromethyl)dimethylsilane sum of isomers394630010, 1 g; 394630050, 5 g75422-66-190%Allyl(diisopropyl)(4-metho xyphenyl)silaneMO01086DA, 1 g216107-40-395%Allyltrichlorosilane31322 0050, 5 g; 313220250, 25 g107-37-995%Allyltrimethoxysilane3889400 50, 5 mL; 388940250, 25 mL2551-83-997+%Allyltrimethylsilane19699 0100, 10 mL; 196990500, 50 mL; 196992500, 250 mL762-72-199%Allyltrimethylsilane3499901 00, 10 mL; 349990500, 50 mL762-72-197%3-[2-(2-Aminoethylamino)eth ylamino]propyl-trimethoxysilane , 25 mL; 346171000, 100 mL; 346175000, 500 mL35141-30-13-Aminopropyldimethylmethoxy silane336600010, 1 g; 336600050, 5 g31024-26-797%3-Aminopropyltriethoxysila ne151080050, 5 g; 151081000, 100 g; 151085000, 500 g; 151080025, kg919-30-299%3-Aminopropyltriethoxysilan e AcroSeal 430941000, 100 mL; 430948000, 800 mL919-30-299%3-Aminopropyltrimethoxysila ne313251000, 100 mL.

10 313255000, 500 mL13822-56-595%Azidotrimethylsilane16793 0100, 10 mL; 167930500, 50 mL; 167932500, 250 mL4648-54-897%BDCS silylation reagent, AcroSeal 200941000, 100 mL; 200948000, 800 mL1185092-02-7N-Benzyl-3-(tert-butyldime thylsilanyloxymethyl)piperid-4-oneMO0791 2DA, 1 g; MO07912DE, 5 g325486-37-195%Benzyloxytrimethylsilane3 91990050, 5 g; 391990250, 25 g; 391991000, 100 g14642-79-694%1,2-Bis(chlorodimethylsily l)ethane313260050, 5 g; 313260250, 25 g13528-93-396%Bis(1H-inden-1-yl)dimethyl silane388480010, 1 g; 388480050, 5 g18666-26-797%Bis(2,3,4,5-tetramethyl-2, 4-cyclopentadiene-1-yl)dimethylsilane388 901000, 100 mg; 388905000, 500 mg89597-05-795+%1,1-Bis(trichlorosilylme thyl)ethylene338650010, 1 g; 338650050, 5 g78948-04-6N,O-Bis(trimethylsilyl)acetam ide156460250, 25 mL; 156461000, 100 mL; 156460011, 1 L10416-59-895%Bis(trimethylsilyl)acetyle ne182010100, 10 g; 182010500, 50 g14630-40-199%Bis(trimethylsilyl)-N-tert -butylacetaldimine330960010, 1 g127896-07-595+%alpha,alpha-Bis(trimethy lsilyl)-tert-butylketimine331165000, 500 mg147227-26-7 Bis(trimethylsilyl)carbodiimide375130010 , 1 g; 375130050, 5 g; 375130250, 25 g1000-70-098%1,4-Bis[(trimethylsilyl)eth ynyl]benzene390620010, 1 g; 390620050, 5 g17938-13-598%N,O-Bis(trimethylsilyl)hyd roxylamine215980010, 1 g; 215980050, 5 g; 215980250, 25 g22737-37-797%Bis(trimethylsilyl) malonate313300100, 10 g; 313300500, 50 g18457-04-098%1,1-Bis(trimethylsilyloxy) -1,3-butadiene331050010, 1 g87121-06-01,2-Bis(trimethylsilyloxy)eth ane209580100, 10 g; 209580500, 50 g7381-30-898%beta,beta-Bis(trimethylsily loxy)styrene330950010, 1 g31491-21-1 Bis(trimethylsilyl)sulfide367370010, 1 g; 367370050, 5 g; 367370250, 25 g3385-94-295%Bis(trimethylsilyl)tellurid e291660050, 5 mL4551-16-098%N,O-Bis(trimethylsilyl)tri fluoroacetamide168000050, 5 g; 168000250, 25 g.