Vol. 9, o. 6 lefin Metathesis Features include: First Generation Grubbs Catalyst
2 Introduction Introduction Yves Chauvin obert. Grubbs ichard. Schrock 2005-1 erisson Chauvin 1971 Figure 2 1 Katz - 3 1990 Schrock 4 1992 Grubbs Grubbs 5 CM CAMCM EM M CM ADMET [M] [M] William Sommer roduct Manager [M] eferences: (1) (a) Schrodi, Y.; ederson,. L. Aldrichimica Acta 2007, 40, 45. (b) Adv. Synth. Catal. 2007, 349, 1 268 (lefi n Metathesis Special Issue). (c) Grubbs,.. Tetrahedron 2004, 60, 7117. (d) andbook of Metathesis; Grubbs,.., Ed.; Wiley-VC: Weinheim, 2003; Vols. 1 3. (e) Trnka, T. M.; Grubbs,.. Acc. Chem. es. 2001, 34, 18. (f ) Fürstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012. (g) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. 1997, 36, 2036. (2) (a) erission, J. L.; Chauvin, Y. Makromol. Chem. 1971, 141, 161. (b) Chauvin, Y. Angew. Chem., Int. Ed. 2006, 45, 3740. (3) Katz T. J.; othchild,. J. Am. Chem. Soc. 1976, 98, 2519. (4) Schrock,.. et al. J. Am. Chem. Soc. 1990, 112, 3875. (5) guyen, S. T. et al. J. Am. Chem. Soc. 1992, 114, 3974. Figure 1 [M] Grubbs - M ADMET CM CM www.sigma-aldrich.com CAS MSDS sigma-aldrich.com/japan M, I aman, UV DF My rofile 1) Web language=japanese, 2) MSDS=English, 3) Country=Japan 3 Submit Web Tel:03-5796-7330 Fax:03-5796-7335 E-mail: sialjpts@sial.com
3 The Grubbs Catalysts Cy 3 Cy 3 Cy 3 579726 Grubbs 1 st generation catalyst 569747 Grubbs 2 nd generation catalyst 682330 Grubbs 3 rd generation catalyst Cy 3 577944 oveyda-grubbs 1 st generation catalyst 569755 oveyda-grubbs 2 nd generation catalyst Cy 3 Cy + 3 -BF 4 707961 iers-grubbs 1 st generation catalyst The Grubbs Catalysts Cy + 3 -BF 4 Cy 3 Cy 3 Cy 3 707988 iers-grubbs 2 nd generation catalyst 578681 682365 Cy 3 682381 682284 682373 Discover ew Cross-Coupling Catalysts 2 d i-r Cy2 2 d Cy2 2 d i-r Cy2 i-r 2 d t-bu 2 i-r i-r i-r i-r i-r 704954 (from Xos) 704946 (from Sos) 707589 (from os) 708739 (from t-buxos) For more information, visit sigma-aldrich.com/buchwald sigma-aldrich.com Tel:03-5796-7340 Fax:03-5796-7345 E-mail: safcjp@sial.com
4 ing-osing Metathesis ing-osing Metathesis C-C 1 1980 Villemin 2 1993 Grubbs 3 Grubbs Scheme 1 4 CM CM 2004 Wood 5 4 20 Wood Scheme 2 2 mol Grubbs 25 mol Grubbs-oveyda 76 Grubbs oveyda-grubbs Grubbs iers iers Grubbs 0 Grubbs 4 25 2 90 Scheme 3 6 0 Grubbs 35 iers 50 M Scheme 4 7 IV Scheme 1 Scheme 2 Scheme 3 Et MB 76% Et Cy 3 Cy3 Cy 3 X (2-4 mol %) C66, 20 C X =, C 1-2 h 93% CF 3 X TBS 89% 85% Cy3 Cy3 (2 mol %) 2C=C2 C22, 25 C (25 mol %) toluene, Δ Cy3 BF4 (1 mol %) CD22, 0 C, 2h ingenol Et 98% Et >90% conversion 25% completion with Grubbs Catalyst (2 nd Generation) MB + 2.2 2C C2 B(C 6F 5) 4 sigma-aldrich.com/japan Scheme 4 Tel:03-5796-7330 Fax:03-5796-7335 E-mail: sialjpts@sial.com
5 Stoltz Grubbs + - 5.5 oveyda-grubbs CM Scheme 5 8 i-bu (5 mol %) benzene, 60 C i-bu 97% (+)-elatol = 22β - CM CM oveyda-grubbs 15-24 9 Scheme 6 Donohoe CM 10 2007 oveyda-grubbs Grubbs TS TFA Scheme 7 Scheme 5 2 1 (10 mol %) 1 toluene, 80 C 1 = TBS, 2 = Me, ; all combinations with 22α- and 22β- 1 =, 2 = Me, ; all combinations with 22α- and 22β- Scheme 6 2 22 15-88% ing-osing Metathesis 2008 - Z - - Z - CM Grubbs 2 CM 72 Scheme 8 11 Et (10 mol %) toluene, 60 C then 1 eq TS 60% 3 C n-bu Cy 3 (10 mol %) toluene, reflux then 0.6 eq TFA 38% Scheme 7 Tel:03-5796-7340 Fax:03-5796-7345 E-mail: safcjp@sial.com
6 ing-osing Metathesis CAM Schrock C-C 12 13 Fürstner 14 CAM Scheme 9 eferences: (1) icolaou, K. C. et al. Angew. Chem., Int. Ed. 2005, 44, 4490. (2) (a) Villemin, D. Tetrahedron Lett. 1980, 21, 1715. (b) Tsuji, J. et al. Tetrahedron Lett. 1980, 21, 2955. (3) Fu, G. C. et al. J. Am. Chem. Soc. 1993, 115, 3800. (4) Fu, G. C. et al. J. Am. Chem. Soc. 1993, 115, 9856. (5) ickel, A. et al. J. Am. Chem. Soc. 2004, 126, 16300. (6) omero,. E. et al. Angew. Chem. Int. Ed. 2004, 43, 6161. (7) omero,. E. iers, W. E. J. Am. Chem. Soc. 2005, 127, 5032. (8) White, D. E. et al. J. Am. Chem. Soc. 2008, 130, 810. (9) Matsuya, Y. et al. rg. Lett. 2009, 11, 3970. (10) (a) Donohoe, T. J. et al. Eur. J. rg. Chem. 2005, 1969. (b) Donohoe, T. J. et al. Tetrahedron 2008, 64, 809. (c) Donohoe, T. J. et al. rg. Lett. 2006, 8, 543. (d) Donohoe, T. J. et al. Chem. Eur. J. 2008, 14, 5716. (11) Donohoe, T. J. et al. Angew. Chem. Int. Ed. 2008, 47, 7314. (12) Schrock,.. Chem. ev. 2002, 102, 145. (13) (a)fürstner, A. et al. Chem. Commun. 2005, 2307. (b) Schrock,.. et al. Adv. Synth. Catal. 2007, 349, 55. (14) Bindl, M. et al. J. Am. Chem. Soc. 2009, 131, 9468. Me TIS Et TS Et Et Me TIS Cy3 (7.5 mol %) C22, Δ Et TIS then TS TIS (85% yield over two steps) Me Me C2Me C 2Me Cy3 (15 mol %) toluene, Δ 72% ( )-(Z)-deoxypukalide Scheme 8 3Si Mo Si3 3Si (20 mol %) sigma-aldrich.com/japan Scheme 9 87% 54% Tel:03-5796-7330 Fax:03-5796-7335 E-mail: sialjpts@sial.com
7 Cross Metathesis 1 2 2000 Corey 3 Scheme 1 Cy3 Cy3 (10 mol %) C2C2, rt Me Me Me Me Cross Metathesis Grubbs o- - oveyda-grubbs 4 Scheme 2 Grubbs oveyda-grubbs 5 mol Grubbs owell β - α- -β - oveyda- Grubbs Grubbs 5 Scheme 3 6 Botta β Grubbs CuS 4 10 3 Scheme 4 7 eferences: (1) Connon, S. J. et al. Angew. Chem. Int. Ed. 2003, 42, 1900. (2) Chatterjee, A. K. et al. J. Am. Chem. Soc. 2003, 125, 11360. (3) (a) Xiong, Z. et al. J. Am. Chem. Soc. 2000, 122, 4831. (b) Xiong, Z. et al. J. Am. Chem. Soc. 2000, 122, 9328. (4) Stewart, I. C. et al. rg. Lett. 2008, 10, 441. (5) Liang, Y.et al. Tetrahedron Lett. 2009, 50, 1020. (6) Diver, S. T. et al. Chem. ev. 2004, 104, 1317. (7) Castagnolo, D. et al. J. rg. Chem. 2009, 74, 3172. Scheme 1 Et Et Ac 89%, >20:1 dr Scheme 2 + Scheme 3 + + Et Et (5 mol %) C22, Δ 91%, >20:1 dr Et (3 x 2 mol %) C22, Δ Cy3 (10 mol %) 2 eq. CuS 4 t-bu/2 1:1 μw, 80 C then, I 2 Bz Et Bz 98%, >20:1 dr MB Et 66%, 3:2 dr 85% E:Z = 1:1 Bz 51% 68% 39% 63% Scheme 4 Tel:03-5796-7340 Fax:03-5796-7345 E-mail: safcjp@sial.com
8 ing-pening Metathesis olymerization M ing-pening Metathesis olymerization M M Ziegler atta M 1 1992 Grubbs M 2 M M M Grubbs Synthesis of ush-like olymers via M Cheng M - Cheng Grubbs DI 1.03 1.15 Scheme 1 3 eferences: (1) (a) Ziegler,. et al. Angew. Chem. 1955, 67, 541.(b) atta, G. Angew. Chem. 1956, 68, 393. (2) guyen, S. T. et al. J. Am. Chem. Soc. 1992, 114, 3974. (3) Lu,. et al. J. Am. Chem. Soc., 2009, 131, 13582. + TMS 1.0 eq Scheme 1 2.5 eq (5 mol %) x TMS n brush-like polymer TF: C22 (9:1) y TMS x y polymerization of amino acid -carboxyanhydride CMU sigma-aldrich.com/japan + C 712191 F6 - For more information, visit sigma-aldrich.com/comu sigma-aldrich.com ATU Tel:03-5796-7330 Fax:03-5796-7335 Ethyl(hydroxyimino)cyanoacetate (XYMA) Bt, At 233412 C At E-mail: sialjpts@sial.com
9 Catalysts andbook of Metathesis, 3 volume set ISB 978-352730616-9 Z551570-1EA 1 ea 69,600 2,6-Diiso pro pyl phenyl imido-neoph yl idene[( S )-( )-BIE] molybdenum(vi), 97.0% (C) [205815-80-1] C 46 61 Mo 2 FW 755.92 purum, ring-closing metathesis catalyst 3C 3C 3C 3C i-r t-bu Mo t-bu i-r C3 C3 73022-100MG-F 100 mg 53,500 Tris(triphenylsilyloxy)molybdenum nitride pyridine complex, 95% C 59 50 Mo 2 3 Si 3 FW 1015.24 contains up to 10 wt. % toluene Si Mo Si Si 719684 100 mg 18,000 oveyda-grubbs Catalyst 1 st Generation [203714-71-0] C 28 45 2 FW 600.61 6,111,121 sigma-aldrich.com/materialicense 577944-100MG 100 mg 10,200 577944-500MG 500 mg 41,600 577944-2G 2 g 124,100 Dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine) ruthenium(ii) [194659-03-5] C 41 74 2 2 FW 800.95 3C C 3 C3 C3 Catalysts Grubbs Catalyst, 2 nd Generation [246047-72-3] C 46 65 2 2 FW 848.97 3C 3C C3 C3 3C 6,111,121 7,329,758 sigma-aldrich.com/materialicense sialjpts@sial.com Materia 569747-100MG 100 mg 12,900 569747-500MG 500 mg 40,000 569747-2G 2 g 112,100 oveyda-grubbs Catalyst 2 nd Generation [301224-40-8] C 31 38 2 2 FW 626.62 3C 3C C3 C3 3C 6,921,735 sigma-aldrich.com/materialicense 569755-100MG 100 mg 13,500 569755-500MG 500 mg 54,800 569755-2G 2 g 159,000 3C C3 C3 C3 5,969,170 sigma-aldrich.com/materialicense 578681-1G 1 g 21,800 578681-5G 5 g 74,500 Dichloro(3-methyl-2-butenylidene)bis(tricyclopentylphosphine) ruthenium(ii) [220883-08-9] C 35 62 2 2 FW 716.79 5,969,170 sigma-aldrich.com/materialicense 578703-1G 1 g 21,800 578703-5G 5 g 69,700 Grubbs Catalyst, 1 st generation [172222-30-9] C 43 72 2 2 FW 822.96 C 3 C3 6,111,121 sigma-aldrich.com/materialicense 579726-1G 1 g 20,700 579726-5G 5 g 74,000 Tel:03-5796-7340 Fax:03-5796-7345 E-mail: safcjp@sial.com
10 [1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro- (benzylidene) (tricyclohexylphosphine)ruthenium(ii) [ C 42 57 2 2 FW 792.87 C3 C3 [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro- [3-(2-pyridinyl-κ )propylidene-κc]ruthenium(ii) [802912-44-3] 3C C3 C 29 35 2 3 3C C FW 597.58 3 3C C3 Catalysts 6,111,121 7,329,758 sigma-aldrich.com/materialicense sialjpts@sial.com Materia 682284-100MG 100 mg 11,300 682284-500MG 500 mg 42,600 682284-2G 2 g 137,400 [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(benzylidene)bis(3-bromopyridine)ruthenium(ii) C 38 40 2 2 4 3C FW 884.54 3C C 3 3C C3 C 3 11/094,102 sigma-aldrich.com/materialicense 682381-100MG 100 mg 11,700 682381-500MG 500 mg 44,800 682381-2G 2 g 135,500 the nium Metathesis Catalysts Kit I sigma-aldrich. com/materialicense sialjpts@sial.com Materia info@materia-inc.com 6,759,537 sigma-aldrich.com/materialicense 682330-100MG 100 mg 10,800 682330-500MG 500 mg 43,200 682330-2G 2 g 130,800 [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro- (3-methyl-2-butenylidene) (tricyclohexylphosphine)ruthenium(ii) C 44 67 22 3C C3 FW 826.97 3C C 3 3C 5,969,170 7,529,758 sigma-aldrich.com/materialicense sialjpts@sial.com Materia 682365-100MG 100 mg 8,200 682365-500MG 500 mg 31,500 682365-2G 2 g 98,700 C 3 C3 C 3 thenium Metathesis Catalysts Kit I Components Grubbs Catalyst, 1 st Generation (Aldrich 579726) 1 G Grubbs Catalyst, 2 nd Generation (Aldrich 569747) 100 MG oveyda-grubbs Catalyst 2 nd Generation (Aldrich 569755) 100 MG oveyda-grubbs Catalyst 1 st Generation (Aldrich 577944) 100 MG Dichloro(3-methyl-2-butenylidene)bis(tricyclohexylphosphine)ruthenium(II) (Aldrich 578681) 1 G Dichloro(3-methyl-2-butenylidene)bis(tricyclopentylphosphine)ruthenium(II) (Aldrich 578703) 1 G [1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(benzylidene) (tricyclohexylphosphine)ruthenium(ii) (Aldrich 682284) 100 MG [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)bis(3- bromopyridine)ruthenium(ii) (Aldrich 682330) 100 MG [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2- butenylidene) (tricyclohexylphosphine)ruthenium(ii) (Aldrich 682365) 100 MG [1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(2- isopropoxyphenylmethylene)ruthenium(ii) (Aldrich 682373) 100 MG [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[3-(2-pyridinyl-κ ) propylidene-κ C ]ruthenium(ii) (Aldrich 682381) 100 MG 687944-1KT 1 kit 133,800 sigma-aldrich.com/japan [1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro- (2-isopropoxyphenylmethylene)ruthenium(II) C 27 30 22 FW 570.52 C3 Tel:03-5796-7330 Fax:03-5796-7335 C 3 6,921,735 sigma-aldrich.com/materialicense 682373-100MG 100 mg 11,400 682373-500MG 500 mg 44,700 682373-2G 2 g 135,500 3C C3 E-mail: sialjpts@sial.com
11 Dichloro(tricyclohexylphosphine)[(tricyclohexylphosphoranyl)- methylidene]ruthenium tetrafluoroborate, 95% C 37 67 B 2 F 4 2 FW 832.66 BF4 - [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro- [(tricyclohexylphosphoranyl)methylidene]ruthenium tetrafluoroborate, 95% [832146-68-6] C 40 60B 2F4 2 FW 858.67 3C C3 3C C 3 C3 3C F F B F F UTI artnership 7,354,140 Materia sigma-aldrich.com/materialicense sialjpts@sial.com Materia info@ materia-inc.com 707961-100MG 100 mg 6,700 707961-500MG 500 mg 26,200 707961-2G 2 g 79,000 UTI artnership 7,354,140 Materia sigma-aldrich.com/materialicense sialjpts@sial.com Materia info@ materia-inc.com 707988-100MG 100 mg 11,000 707988-500MG 500 mg 43,000 707988-2G 2 g 130,000 Catalysts TurboGrignards for al/mg Exchange of Aryl and eteroaryl Compounds Knochel-auser-Base for Selective Deprotonations FG Mg Li = Mg Li (TurboGrignard) FG = alkyl, alkenyl, ', C 2 ', C, 2, halogen C 3 3 C Mg Li 656984 FG Mg Li 703486 Mg Li 3 C 3 C C 3 C 3 Mg Li 703540 TF Sold in partnership with Selective 1,2-Additions La 3 /Li 703559 TF For more information, visit sigma-aldrich.com/metalations sigma-aldrich.com Tel:03-5796-7340 Fax:03-5796-7345 E-mail: safcjp@sial.com
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