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1、About Tetrodotoxin (TTX)-1Synthesis of TetrodotoxinooNa 予口力一u,力工及，夕口力二笈力盲覆殖（071士毒性在持t:玄131909,ordertertiary secondary primary1. a simple one-step mechanism (three-center cyclic transition state)2. a free-radical processRH + : CH22 R. + - CH2-HRCH2HMeI.PivCI, Py,THF 85% (3 steps)2.H2, Pd-C,THF MeOH,
2、rt, 88%3. (COCI)2, cat. DMF then, CH2N2, CH2CI2j 63-70%Rh2(HNCOCRh3)4 (1.5 mol%)MeI.NH3BH3, CH2CI2/MeOH 75% (2 steps)2. H；, (1200 psi) Rh-C (5 mol%) TFA/MeOH77% (2 steps)Me1.Me2NH,THF83%2. cat. TPAP, NMO, 4 A MS, CH2CI2, 94%Zn (2 eq) CH2I2, TiCI4, cat. PbCI2THF72%Du Bois Synthesis (2003)Hinman, A.;
3、Du Bois, J. J. Am. Chern. Soc.如03, 125, 11510-11511.OMeMeMe2- -BuNH2 BH3,O94aMe 土 MeMe2Ns1 -CH2CI2, rto 又 CI3CO78% (2 steps)Kocovsky, P. Tetrahedron Lett. 1986, 27, 5521-5524.093%2. MeSO2CI, Py, CICH2cH2cl 86%Me MeOoo1. O3, then NaBH4CH2CI2/MeOH, 83%Me MeZn MeOH Du Bois Synthesis (2003)Hinman, A.; D
4、u Bois, J. J. Am. Chern. Soc.如03, 125, 11510-11511.10 mol% Rh2(HNCOCF3)4Phl(OAc)2, MgOC6H565 nitreneCH insertionOAOnitreneimidoiodobenzenespin, C G ; Du Bois, J. Angew. Chem.f Int. Ed. 2001, 40, 598-600.Yamada, Y.; Yamamoto, T.; Okawara, M. Chem. Lett. 1975, 361-362.1. NaSePh,OONH，Me95%BocN=NHBocSMeHgCI2, Et3NMeCN, CH2CI280%BocN32%tetrodotoxin4,9-a n hy d r o tet ro do to x i n32%Kishis synthesisSummaryIsobes synthesis0.49% (28 steps)asymmetric synthesisoverman rearrangementring-openingof epoxide0.25% (39 steps)Du Bois synthesisnitrene CH aminationaldol