FAMS MT FAMS S Formaldehyde Dimethyl Dithioacetal S-xide FAMS DMS α DMS SDMS
H 3 SH 3 S K 2 3 or Pyr. H 3 SH 2 l 3 Sa H 3 SH 2 S 4 Finkelstein FAMS FAMS FAMS FAMS H 2 2 H 2 + MeSH H+ H 2 1 (FAMS) 5 MT FAMS p p MT DMS p H 3 SH 3 Ac 2 [ H 3 SH 2 Ac ] 5 TolS 2 a 2 AcH (Aca) DMS p MT one-potmt
FAMS MT FAMS FAMS MT MT TMA MT FAMS MT
(H 2 ) n 1 2 H 3 + 1 2 H 3 + ah 2 X hν 1 H H 2 (H 2 ) n 1 1 Me H H 2 2 SMe X 1 H H + /MeH ah (H 2 ) n 1 X ah X Ar ArH H H 2 2 H 2 abh 4 H + /MeH ArH 2 H Ar 1 H Me H 2 H BuLi/TMSl Me 1 1 3 n n 2 1 2 X ah 1 Si 2 2 3 1 H H 3 + 2 ArH 2 1 TolS 2 2 2 X ah 1 3 TolS 2 H 2 MT X + H 2 2 TMA 50% ah-toluene 91-99% H H ah/dmf 'X rt / 0.5 h rt / 20-50 h (50-60 / 3 h) ' H + /MeH reflux / 2-3 h ' H + : 4 Hl or H 2 S 4 PhH 2 Me n- 12 H 25 'X MeI n- 6 H 13 Br PhH 2 Br MeI 96 % 92 % 85 % 90 %
MTS,S S,S MT H K 2 3 /iprh H 2 2 H 2 X ah H 2BuLi/TMSl H 2 H 1) S 2 l 2 2) H 6 MT S,S α H 2 H H 2 6 7 S 2 Me S,S p TolS 2 captodative Y Y H H 6 8
THF THF α THF α 6 hν Ph 2 'I ah ' 4 H 2 S 4 MeH ' =Ph, '=Me 85% aney i a-eth Me THF =Me 94% =Ph 98% =Ph 82% =Ph 80% S,S PS H H (Me) 2 Me 2 hν, Ph 2 PTS MeH 77% ()-(E)-9 81% H MeS (2S, 3) aney-i 90% hν (254 nm) ether-h 2 (19:1) 44% (Me) 2 Me 2 PTS H ah 3 75% H 1) a, a 2 HP 4, EtH, 2) PTS, MeH 81% H H H
S,S MPBA MPBA MPBA S 2 Me MPBA (2 equiv) MPBA 10 6 7 S 2 Me S 2 Me 7 u or :uh S 2 Y u Y=Me or Tol u u α ω S 2 Me H '' or H 2 '' (A) Hl 3, rt H 2 '' '' '' '' or H H (A) 7 11 12 α α
7 S 2 Me H 2 H 2 Hl 3, rt H H diamine (mol-equiv.) (h) (%) Et 2.4 21 92 Ph 3.6 24 96 7 S 2 Me H 2 H 2 Hl 3, rt H H H S 2 Me diamine (mol-equiv.) (h) (%) Et Ph 2.4 1.2 5 10 95 78 π π π π MeS TolS 2 H S Ar 15 S H H + /ArH 2 S S S S 13 Ar 14 a: EWG H b: EWG H () c: EWG H () 2 S Ar S 16 EWG
π S,S EWG EL EL EWG S,S nm EWG ma EWG S,S EL DMF Y Y Y S S 17 (a) (b) (c) (a) 17 (Y=n-Pr) (b) 17 (Y=F) (c) 17 (Y= 14 H 29 )
THF λmaxnm ev nm π 17 (Y=F) p (a) (b) 17 (Y=Me) (a) (b)
p H H p p (a) (b) 17 (Y=n- 14 H 29 ) (a) (b) Y p Y S S 18
Y p (a) (c) (b) 17 (Y=H 3 ) πp π (a) Y (b) S 19 19 (Y=H 3 ) 1) G. Tsuchihashi, K. gura, Bull. hem. Soc. Jpn. 1971, 44, 1726. 2) K. gura, G. Tsuchihashi, J. hem. Soc., hem. ommun. 1970, 1689. 3) K. gura, G. Tsuchihashi, Bull. hem. Soc. Jpn. 1972, 45, 2203. 4) D. T. Gibson, J. hem. Soc. 1932, 1819. 5) K. gura,. Yahata, J. Watanabe, K. Takahashi, H. Iida, Bull. hem. Soc. Jpn. 1983, 56, 3543.
6) Encyclopedia of eagent for rganic Synthesis, vol. 4, pp. 2584-2586 (Wiley, 1995). 7) Encyclopedia of eagent for rganic Synthesis, vol. 5, pp. 3589-3591 (Wiley, 1995). 8) K. gura, G. Tsuchihashi, Tetrahedron Lett. 1971, 12, 3151-3154. 9) K. gura and G. Tsuchihashi, Tetrahedron Lett. 1972, 13, 1383-1386; K. gura, Y. Ito and G. Tsuchihashi, Bull. hem. Soc. Jpn. 1979, 52, 2013. 10) K. gura, K. htsuki, M. akamura,. Yahata, K. Takahashi, H. Iida, Tetrahedron Lett. 1985, 26, 2455. 11) K. gura, K. htsuki, K. Takahashi, H. Iida, hem. Lett. 1986, 1597. 12) K. gura,. Sumitani, A. Kayano, H. Iguchi, M. Fujita, hem. Lett. 1992, 1487. 13) K. gura, A. Yanagisawa, T. Fujino, K. Takahashi, Tetrahedron Lett. 1988, 29, 5387. 14) K. gura, A. Kayano,. Sumitani, M. Akazome and M. Fujita, J. rg. hem. 1995, 60, 1106-1107. 15) A. Kayano, M. Akazome, M. Fujita, K. gura, Tetrahedron 1997, 53, 12101. 16) K. gura, T. Arai, A. Kayano, M. Akazome, Phosphorus, Sulfur and Silicon 1999, 153-154, 391. 17) S. Matsumoto, M. Ishii, K. Kimura, K. gura, Bull. hem. Soc. Jpn. 2004, 77, 1897. 18) Y. Sugiyama, Y. Suzuki, S. Mitamura, Y. Kawamoto, M. Fujita, K. gura, Bull. hem. Soc. Jpn. 1994, 67, 3346. 19) K. gura, H. Yanai, M. Miokawa, M. Akazome, Tetrahedron Lett. 1999, 40, 8887. 20) K. gura, M. Miokawa, M. Fujita, H. Ashidaka, A. Mito, onlinear ptics 1995, 13, 253. 21) H. Yanai, D. Yoshizawa, S. Tanaka, T. Fukuda, M. Akazome, K. gura, hemisty Lett. 2000, 238. 22) K. gura,. Zhao, H. Yanai, K. Maeda,. Tozawa, S. Matsumoto, M. Akazome, Bull. hem. Soc. Jpn. 2002, 75, 2359. 23). Zhao, S. Matsumoto, M. Akazome, K. gura, Tetrahedron 2002, 58, 10233. 24) K. gura,. Zhao, M. Jiang, M. Akazome, S. Matsumoto, K. Yamaguchi, Tetrahedron Lett. 2003, 44, 3595. 25). Zhao, M. Akazome, S. Matsumoto, K. gura, Tetrahedron 2002, 58, 10225. (eceived ct. 2005) Katsuyuki gura BSJ SH 3 H 2 SH 3 SH 3 H 2 S 2 H 3