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Transcription:

MCM-41 M41 MCM-41 M41 2

3 m 2 /g nm nm

Mn Ti Ti H N 2 S Ti-MCM-41, H H N H H 2 2 -Urea, CH 2 Cl 2, H 2 S + S 1b 2b 3b 54%, 58% ee Ti M41 H 2 As 4 ZP 4

ZP ZS ZS 5

Me Me Me Me M41 / 15 mg MeH 1.0 mmol 89% Yield(GC) nm nm Kaliaguine Kevan B-M41 Ni-M41 M41 M41 6

R 1 CH or Me R 1 Me SiMe 3 R + M41 CH 2 Cl 2 R 1 M41 Entry Electrophile Enolate MCM-41 / mg/mmol Reaction Conditions Product Yield(%) Me Me Me 1 3 Ph H 1 30 0 C, 6 h Ph 84 Me Me Me 2 6 Ph H 1 50 25 C, 12 h Ph 64 Me Me Me 3 1 30 25 C, 12 h 90 Me Me 4 8 1 50 25 C, 3 h Ph Ph Me 93 97 a 85 b 87 c 90 d entries 1 and 3 entries 2 and 4 a b c d 7

M41 Silica gel 60 M41 M41 Al Si/Al = 190 280 M41 mmol M41 M41 nm 2 H + Me M41 / 90 mg 180 C, 16 h C 5 H 11 Me C 5 H 11 1.0 mmol 5.0 ml 85% Yield HZSM-5 M41 M41 M41 M41 8

Acid Product Isolated Yield(%) C 2 H 5 H C 2 H 5 Me 33 C 3 H 7 H C 3 H 7 Me 68 C 5 H 11 H 4 C 15 H 31 H C 5 H 11 C 15 H 31 Me Me 85 78 i C 3 H 7 H i C 3 H 7 Me 68 H Me 76 Ph H Ph Me 66 M4 M41 M41 M41 + 1-C 8 H 17 Cl or 1-C 8 H 17 H M41 / 100 mg 210 C C C 1 2 C 3 C 7 C 6 C 5 C 4 9

h µmol g 1 µmol g 1 µmol g 1 µmol g 1 µmol g 1 µmol g 1 M41 mmol g 1 Al µmol g 1 M41 n-c 8 H 17 Cl Ni/Si 2 M41 Ni-M41 Ni-M41 10

Ni-M41 ETP Ni-M41 Ni M41 Ni Mo W Re Ni Ni M41 LH 11

M41 M41 V 2 5 /aq.h 2 2 M41 cis cis V ion (12 µmol) M41(100 mg) aq. H 2 2 (1 eq.) 1,4-Dioxane (2.0 ml) r.t. 12 h cis-diol trans-diol H H H H p cis cis de cis cis σ cis trans σ de cis M41 M41 H 2 S 4 12

CREST 11) 1) A. Corma, Chem. Rev., 97, 2373 (1997); G. Soler-Illia, C. Sanchez, et. al., Chem. Rev., 102, 4093 (2002). 2),, 41, 31 (1999);, 62, 411 (2004);, 27, 628 (2004);, 58, 545 (2005). 3) M. Iwamoto, Y. Tanaka, Catal. Surv. from Jpn., 5, 25 (2001). 4) M. Yonemitsu, Y. Tanaka, M. Iwamoto, J. Catal., 178, 207 (1998). 5) M. Iwamoto, Y. Tanaka, J. Hirosumi, N. Kita, Chem. Lett., 2000, 226; M. Iwamoto, Y. Tanaka, J. Hirosumi, N. Kita, S. Triwahyono, Micro. Meso. Mater., 48, 271 (2001). 6) M. Iwamoto, T. Abe, Y. Tachibana, J. Mol. Catal. A, 155, 143 (2000). 7) P. Wu, M. Iwamoto, Chem. Lett., 27, 1213 (1998); P. Wu, M. Iwamoto, Chem. Mater., in press. 8) M. Iwamoto, H. Kitagawa, Y. Watanabe, Chem. Lett., 31, 814 (2002); H. Takada, Y. Watanabe, M. Iwamoto, Chem. Lett., 33, 62 (2004). 9) Y. Tanaka, N. Sawamura, M. Iwamoto, Tetrahedron Lett., 39, 9457 (1998). 10) M. Iwamoto, Y. Tanaka, N. Sawamura, S. Namba, J. Am. Chem. Soc., 125, 13032 (2003). 13

12) D. Trong, P. N. Joshi, G. Lemay, S. Kaliaguine, Stud. Sur. Sci. Catal., 97, 543 (1995). 13) M. Hartmann, A. Poppl, L. Kevan, J. Phys. Chem., 100, 9906 (1996). 14) T. Yamamoto, T. Tanaka, T. Funabiki, S. Yoshida, J. Phys. Chem. B, 102, 5830 (1998); A. Ito, T. Kodama, S. Maeda, Y. Masaki, Tetrahedron Lett., 39, 9461 (1998). 15) S. Murata, M. Suzuki, R. Noyori, Tetrahedron, 44, 4259 (1988); T. Sato, J. tera, H. Nozaki, J. Am. Chem. Soc., 112, 901 (1990); J.-X. Chen, K. Sakamoto, A. rita, J. tera, Tetrahedron, 54, 8411 (1998). 16) M. Kawai, M. naka, Y. Izumi, Bull. Chem. Soc. Jpn., 61, 1237 (1988). 17) H. Ishitani, M. Iwamoto, Tetrahedron Lett., 44, 299 (2003). 18) G. A. lah, Friedel-Crafts and Related Reactions, Willey, New York, 1963. 19),,,, 45, 522 (2003). 20) (a). L. Wang, Y. Ma, X. Ji, H. Yan, Q. Qiu, J. Chem. Soc., Chem. Commun., 1995, 2307. (b) J. Kaur, I. V. Kozhevnikov, J. Chem. Soc., Chem. Commum., 2002, 2508. (c) M. Hino, K. Arata, J. Chem. Soc., Chem. Commun., 1985, 112. 21),,,, 47, 467 (2005). 22) S. H. Sharman, J. Am. Chem. Soc., 84, 2945 (1962); R. M. Roberts, E. K. Baylis, G. J. Fonken, J. Am. Chem. Soc., 85, 3454 (1963). 23),,, pp 31-37, (2001);, 56, 29 (2003); A. M. Al-Jarallah, M. A. B. Siddiqui, A. M. Aitani, A. W. Al-Sa doun, Catal. Today, 14, 1 (1992); T. Cai, Catal. Today, 51, 153 (1999). 24),,, 74, 295 (1953); J. R. Sohn, A. zaki, J. Catal., 59, 303 (1979). 25) P. P. Nill, J. J. Rooney, J. Am. Chem. Soc., 94, 4383 (1972); T. Yamgaguchi, Y. Tanaka, K. Tanabe, J. Catal., 65, 442 (1980). 26) R. H. Grubbs Ed., Handbook of Metathesis, Wiley-VCH Verlag BmbH & Co., Weinheim, 2003. 27), (2004);, M, D,, 26, 484 (2003). 28),,, A, 3J20 (2005). 29) L. Doan, D. Whalen, J. rg. Chem., 64, 712 (1974). 30) A. Taguchi, T. Abe, M. Iwamoto, Adv. Mater., 10, 667 (1998); Micro. Meso. Mater., 21, 387 (1998). 31) H. kada, N. Nakajima, T. Tanaka, M. Iwamoto, Angew. Chem. Int. Ed., in press. 32),, 28, pp 77-93 (2005). (Received Jan. 2006) Masakazu Iwamoto Crompton Lanchester Medal 14