寄稿論文 新光延試薬 | 東京化成工業

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1 DEAD TPP A Et C C Et Et C C Et 2 A A ex. ucleophiles (A) P 3 P 3 1 xygen itrogen Carbon Sulfur C 3 S Ts Tf Scheme 1. TPP DEAD TPP DEAD redox condensation Walden Bz Tf DEAD-TPP 87% Tf Bz Scheme 2.

2 pk a pk a (i) pk a < 11 Et (ii) 11 < pk a < 13 (pk a = 8.3) DEAD-TPP 91% Et Ts (pk a = 11.7) DEAD-TPP 51% Ts (iii) pk a > 13 Et Et (pk a = 13.3) DEAD-TPP 0% Et Et Scheme 3. path a Et C C Et P 3 Et desired reaction Et Et (path a) side reaction (path b) 3 P 3 Et Et 4 Et 4 A P 3 A P A 1 2 A Et C C Et 6 2 Scheme 4.

3 A A path b pk a A DEAD,,','-tetraisopropylazodicarboxamide TIPA 1,1'-(azodicarbonyl)dipiperidine ADDP,,','-tetramethylazodicarboxamide TMAD C C TIPA Et Et 4 7 C C ADDP δ ' ' 2 ' δ C C TMAD DTD Scheme 5. 1,6-dimethyl-1,5,7-hexahydro-1,4,6,7-tetrazocin-2,5-dione DTD DEAD TBP Bu 3 P PBu 3 PBu 3 PBu Scheme 6. DEAD Ts 10 (pk a = 11.7) C C - PBu C, 24 h Ar, dry in sealed tube 62% Ts Scheme 7.

4 ' C P 3 C ' ' C C ' 2 P 3 ' C " P 3 X C P 3 X C P Ylide osphorane Scheme 8. A A A-' X C 3 X P 3 A ' P 3 A ' A ' P 3 Scheme 9. (cyanomethylene)tributylphosphorane CMBP (cyanomethylene)trimethylphosphorane CMMP CMMP C PBu 3 C P 3 (cyanomethylene)tributylphosphorane (cyanomethylene)trimethylphosphorane ( CMBP ) ( CMMP ) Scheme 10. DEAD

5 DEAD DEAD C C C C C C 17 Scheme 11. CMBP CMMP CMBP CMMP mmol TF Wittig CMMP A C P' 3 A C 3 P' 3 CMBP: = Bu CMMP: = Scheme 12.

6 S 2 ' 1) Base 2) ''-X S 2 ' '' ' '' Scheme 13. pk a pk a pk a DEAD pk a TIPA ADDP TMAD DTD CMBP CMMP CMBP CMMP Table 1. eaction of -thyl-p-tosylamide (10). % yield - DEAD-TPP *) Ts 10 (pk a = 11.7) edox system, temp., 24 h edox system temp. TIPA-TBP ADDP-TBP TMAD-TBP DTD-TBP CMBP r.t. r.t. r.t. r.t. r.t. r.t. 100 C Ts CMMP r.t. 80 C *) The reaction was carried out in TF. pk a Ts 2 P 3 DEAD Ts P 3 18 TF, 0 C 98% 19 Scheme 14.

7 , CMMP CMBP Table 2. eaction of p-tosylamide (18). 18 (1.5 eq) CMBP, temp., 24 h Ts (Ts 2 ) r.t. 80 C yield (%) yield (%) 93 a) (22) 85 (12) a) : no experimental result pk a pk a pk a pk a 20 (pk a = 11.2) 51% Et 21 (pk a = 10.7) 42% Et Et Et Et 22 (pk a = 13.3) 0% Scheme 15. Et Et

8 pk a DTD CMBP DTD DTD CMBP CMMP CMMP CMMP CMMP cis Table 3. eaction of enylsulfonylacetonitrile (23). S 2 edox system (1.5equiv.), temp., 24 h S 2 S 2 % yield 23 (pk a = 12.0) edox system DEAD-TPP TMAD-TBP DTD-TBP CMBP r.t. r.t. r.t. r.t. 100 C 120 C CMMP 100 C 57 (22) 59 (3) 46 (51) 75 (21) 72 (28) 1) 64 (16) 52 (22) ex ) : no experimental result. S 2 CMMP, 100 C, 24 h S % 23 CMMP (3 equiv.), 100 C, 24 h C S % Scheme 16.

9 pk a pk a MT pk a CMBP CMMP Table 4. eaction of MT Sulfone (28). S S 2 Tol edox system (1.5equiv.), temp., 24 h S S 2 Tol 28 (pk a = 23.4) % yield edox system TMAD-TBP r.t. DTD-TBP r.t. r.t. CMBP 100 C 120 C 150 C CMMP 100 C ) 40 2) 41 1) < ex 1) : no experimental result <1 2 2) 56 2) ) Dimeric ether was obtained pk a S 2 (pk a = 23.4) CMMP TF, 80 C, 24 h S 2 90% C (pk a = 18.5) S 2 ex CMMP (3.0 equiv.) TF, 80 C, 24 h 100% C ex S 2 S 2 (pk a = 16.7) ex CMMP TF, 120 C, 24 h 100% ex S 2 Scheme 17.

10 pk a CMMP S 2 CMMP DME, 100 C, 24 h 100% Bu S 2 CMMP ex ex DME, 120 C, 24 h S 2 76% Scheme 18. Walden pk a pk a C C ' DEAD-TPP ' or ' Scheme 19. pk a C Bz 29 DEAD-TPP 27% C DEAD-TPP no reaction 30 Scheme 20.

11 TMAD p p p pk a p DEAD TMAD p DEAD 29 C TMAD-TBP 0 C, 10 min, then 60 C, 24 h = - : 98% (31 / 32 > 99.5 / 0.5) = 2 - : 28% (31 / 32 = 45 / 55) Scheme C TMAD-TBP 0 C, 10 min, then 60 C, 24 h 39% Scheme 22. Prashad CMBP 18 (2 equiv.) CMBP (3 equiv.), r.t. 71% Ts (1 equiv.) CMBP, r.t. (1 equiv.) CMBP, 100 C 71% Ts Scheme

12 Walden S C % ee 23 CMBP 120 C, 24 h, 79% S 2 C 6 13 C 6 13 >95% ee C C C % ee TolS 28 2 S CMBP C C C, 24 h, 98% ee 71% Scheme 24. C TBS S 2 12 CMMP TF, 100 C, 24 h 91% S 2 TBS 11 Ts TMAD-PBu 3 S 2 11, r.t., 24 h 100% 11 Theonelladine D S 2 Ts 11 TMAD-PBu 3 Tol., r.t. 84% Theonelladine C 2 11 Scheme 25. norfaranal norfaranal anti S S

13 MPM 23 CMMP Tol., 100 C, 24 h 79% MPM S 2 1) DEAD-P 3, C S 2 CMMP 2) 1 a, ex. / (1 / 3) 98% 100 C, 24 h 54% S 2 norfaranal Scheme S 1) Bn, TMAD-TPP, C 2 Cl 2 2) S, K 2 C 3, DMF > 95% Bn S 2 1) Bn, TMAD-TBP, TF 2) 95% TFA / water high yield S 2 2 Scheme 27. staff SUB GAT

14 1). Mitsunobu, Synthesis, 1981, 1. 2) D. L. ughes, The Mitsunobu eaction. rganic eactions, Vol. 42, eds. by P. Beak, et al., John Wiley & Sons, Inc., ew York, 1992, p ) M. L. Edwards, D. M. Stemerick, J.. McCarthy, Tetrahedron Lett., 31, 3417 (1990). 4) M. Wada,. Mitsunobu, Tetrahedron Lett., 13, 1279 (1972). 5) S. Itô, T. Tsunoda, Pure & Appl. Chem., 71, 1053 (1999). 6),,, 52, 113 (1994). 7) T. Tsunoda, Y. Yamamiya, S. Itô, Tetrahedron Lett., 34, 1639 (1993). 8) T. Tsunoda, J. tsuka, Y. Yamamiya, S. Itô, Chem. Lett., 1994, ) T. Tsunoda,. Kaku,,,','-Tetramethylazodicarboxamide. Electronic Encyclopedia of eagents for rganic Synthesis eds. by L. A. Paquette, et al., Wiley, 15 ctober ) T. Tsunoda, M. agaku, C. agino, Y. Kawamura, F. zaki,. ioki, S. Itô, Tetrahedron Lett., 36, 2531 (1995). 11) T. Tsunoda, F. zaki, S. Itô, Tetrahedron Lett., 35, 5081 (1994). 12) T. Tsunoda, C. agino, M. guri, S. Itô, Tetrahedron Lett., 37, 2459 (1996). 13) I. Sakamoto,. Kaku, T. Tsunoda, Chem. arm. Bull., 51, 474 (2003). 14) T. Tsunoda,. Takagi, D. Takaba,. Kaku, S. Itô, Tetrahedron Lett., 41, 235 (2000). 15) J.. enry, L.. Marcin, M. C. McIntosh, P. M. Scola, G. D. arris, Jr., S. M. Weinreb, Tetrahedron Lett., 30, 5709 (1989). 16) G. Dauphin, A. Kergomard, Bull. Soc. Chim. Fr., 1961, ) S. Bittner, Y. Assaf, P. Krief, M. Pomerantz, B. T. Ziemnicka, C. G. Smith, J. rg. Chem., 50, 1712 (1985). 18) T. Tsunoda,. Yamamoto, K. Goda, S. Itô, Tetrahedron Lett., 37, 2457 (1996). 19) S. Ji, L. B. Gortler, A. Waring, A. Battisti, S. Bank, W. D. Closson, P. Wriede, J. Am. Chem. Soc., 89, 5311 (1967); J. Kovacs, U.. Ghatak, J. rg. Chem., 31, 119 (1966); E.. Gold, E. Babad, J. rg. Chem., 37, 2208 (1972); E. Vedejs, S. Lin, J. rg. Chem., 59, 1602 (1994). 20) T. Tsunoda, K. Uemoto, T. htani,. Kaku, S. Itô, Tetrahedron Lett., 40, 7359 (1999). 21) K. Uemoto, A. Kawahito,. Matsushita, I. Sakamoto,. Kaku, T. Tsunoda, Tetrahedron Lett., 42, 905 (2001). 22) S. F. Martin, J. A. Dodge, Tetrahedron Lett., 32, 3017 (1991); J. A. Dodge, J. I. Trujillo, M. Presnell, J. rg. Chem., 59, 234 (1994). 23). Loibner, E. Zbiral, elv. Chim. Acta, 60, 417 (1977). 24) M. Saïah, M. Bessodes, K. Antonakis, Tetrahedron Lett., 33, 4317 (1992). 25) T. Tsunoda, Y. Yamamiya, Y. Kawamura, S. Itô, Tetrahedron Lett., 36, 2529 (1995). 26) M. Prashad, F. J. Kathawala, T. Scallen, J. d. Chem., 36, 1501 (1993). 27) T. Suzuki, J. zaki,. Sugawara, Agric. Biol. Chem., 47, 869 (1983). 28) E. edenström,.-e. ögberg, A.-B. Wassgren, G. Bergström, J. Löfqvist, B. ansson,. Anderbrant, Tetrahedron, 48, 3139 (1992). 29) J. Kobayashi, T. Murayama, Y. hizumi, T. Sasaki, T. hta, S. ozoe, Tetrahedron Lett., 30, 4833 (1989). 30) K. Mori,. Ueda, Tetrahedron Lett., 22, 461 (1981); K. Mori,. Ueda, Tetrahedron, 38, 1227 (1983); L. Poppe, L. ovák, P. Kolonits, Á. Bata, C. Szántay, Tetrahedron, 44, 1477 (1988). 31) S.. Chhabra, A. Mahajan, W. C. Chan, J. rg. Chem., 67, 4017 (2002). 32) J. J. Scicinski, M. D. Barker, P. J. Murrary, E. M. Jarvie, Bioorg. d. Chem. Lett., 8, 3609 (1998).

15 IUPAC IUPAC

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