Keisuke Suzuki. Baran lab Group Meeting 6/11/16. Shigenobu Umemiya. Akira Suzuki. Takanori Suzuki (Hokkaido University)
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1 197.D., Teruaki Mukaiyama, University of Tokyo 193 Assistant Professor, Keio University 197 Lecturer, Keio University 199 Assocate Professor, Keio University 1990 Visiting Professor, ET 1994 ull Professor, Keio University 1996 ull Professor, Tokyo nstitute of Technology Award (Selected) 196 The Chemical Society of Japan Award (for young chemist) 1999 agoya Silver dal Award 2003 The Society of Synthetic rganic Chemisty, Japan Award 200 umboldt Award (Germany) 200 The Chemical Society of Japan Award 20 dal with Purple ibbon 2014 Japan Academy Prize Akira Suzuki Baran lab Group eting 1 X 2 BY 2 Pd 0 (cat.), ligand, base Takanori Suzuki (okkaido University) 1 2 ACE, 2014, 3, 70. Eiichi akamura (University of Tokyo) Science, 2001, 291, Kouichi arasaka ab 4 2 B() Masahiro Murakami (Kyoto University) ' ' Tetrahedron, 194, 40, Shu Kobayashi (University of Tokyo) ligand Pr(Tf) 3 Masahiko Yamaguchi (Tohoku University) ' ' aq. JACS, 2003, 12, 299. samu Shiina (Tokyo University of Science) 2 uyou Mitsunobu 2 CL, 2002, 26. Yujiro ayashi (Tohoku University) ACE, 200, 44, ACE, 200, 47, 202. obuharu wasawa (Tokyo nstitute of Technology) C 2 ligand [h], [Al] Takahiko Akiyama (Gakushuin University) P C 2 JACS, 2011, 133, 121. cat. [h] [h] ature, 1994, 370, P 3 DEAD BCSJ, 1967, 40, 93. ACE, 2004, 43, 166.
2 Baran lab Group eting Asymmetric pinacol-type rearrangement >99% ee 1 3%, >99% ee EE Ms, 3, 0 o C 1 =aryl, vinyl 77%, >99% ee 3 steps 3 Al, -7 o C 7%, >99% ee 1 2 Tetrahedron Lett. 193, 24, B 3 T, -7 o C Ms, 3, 0 o C S Al Al, -7 o C % DBAL- -7 o C 1) (C) 2, DMS 3, -7 o C Ms 2) C=CC 2 Cr 2, 0 o C 72% EE 2 2 then 2 S 4 EE 92% BM EE Ms 3 Al -7 o C to -20 o C % (3 steps) =BM 3 Al -7 o C 0% ' '= quant. '=Ms EE Total synthesis of protomycinolide V (+)-eldanolide Tetrahedron Lett. 19, 26, EE 9 A A n-bu 9 hexane EE 0 o C EE 91% protomycinolide V J. Am. Chem. Soc. 196,, 221.
3 Epoxy silyl ether rearrangement substrate product Ti 4, -7 o C % 3 Al -7 to -0 o C 7% 1) Co(C) 3 2) Tf, 3) CA, Bn Co-complexed alkynyl group -an excellent migrator- Ms (C) 3 Co glycosyl donors Co(C) 3 Bn 6% 79% J. Am. Chem. Soc. 196,, 327. (C) 3 Co Co(C) 3 Co-complex >> 90%, 3 steps J. Am. Chem. Soc. 1996, 11, 949. Glycosylation -one of the oldest but unresolved problems- X X =,,,, S, S 2, P()() 2, Ac, Ms, Se, etc. eview, see; :Chem. ev. 1993, 93, 103. C :Tetrahedron 199, 4, C 3 Schmidt ACE, 190, 19, 731 S Mukaiyama CL, 2003, 32, Ac Ac Entry tallocene Cp 2 Ti 2 Cp 2 Zr 2 Cp 2 f 2 Cp 2 M 2 Ag 4 = cyclohexamethanol Solvent t Bu Ac Conditions 0 o C, 2 h -20 o C, min -20 o C, 30 min Cp 2 Zr 2 Ag 4 solvent Conditions Ac -20 o C, 40 min Baran lab Group eting Cp 2 Zr 2 -Ag 4 -an efficient activator of glycosyl fluorides α Yield 90% 90% 6% t Bu α Yield 93% 20 o C, 30 min 9% Ac Ac β α : β 1 : : : 1 β α : β 1.4 : 1 0 : 1 t Bu Caution : Ag 4 is potentially explosive. Tetrahedron Lett. 19, 29, 367. Modified condition : Cp 2 f 2, AgTf (less reactive but much safer) Angew. Chem. nt. Ed. 200, 44, 371. Total synthesis of mycinamicin V Ac Cp 2 Zr 2 Ag 4 21 =sugar, rt 6% Ac 21 Tetrahedron Lett. 19, 29, 37. mycinamicin V
4 earrangement of -Glycoside to C-Glycoside Step 1 0 mol% activaor Tf T, -7 o C min =, MM, Bn 74~2% Bn Bn T -7 o C % Bn Bn Ac Bn Bn Bn Bn Step 2 Cp 2 f 2 Ag 4 4ÅMS -7 o C to -20 o C 3 steps, -20 o C B % 14% Sn 4 67% 11% Cpf 2 -Ag 4-76% Tetrahedron Lett. 19, 29, 693. [2+4] cycloaddition -an efficient generation of aryne- Total synthesis of (+)-gilvocarcin M Tetrahedron Lett. 1991, 32, 673. Bn Bn Bn Bn 7%, α:β = :1 Tf (+)-gilvocarcin M J. Am. Chem. Soc. 1992, 114, 36. [2+2] cycloaddition of benzyne and ketene silyl acetal Bn Bn Si n Si3 3 Bu Entry Tf Bn ' TBS TBS C C ' eductant Sm 2 Sm 2, MPA Ti 4, Zn Conditions 0 o C T, -7 o C Sm 2 -mediated pinacol cyclization Yield 99% 93% Baran lab Group eting trans/cis >99 : 1 >99 : 1 20 : 1 4 Ti 4, Mg(g) 94% 16 : 1 C 2 MM Sm 2 C C >99% ee 1) aq. 2) () 3 C PTSA 3) S 3 Py, 3 DMS T, 0 o C 64-90% =,, alkyl '=alkyl, Bn MM ' ' C 2 Synlett 199, 177. elv. Chim. Acta 2002,, 39. inductive effect C C Chiral Transmission Bn >99% ee Bn Angew. Chem. nt. Ed. 1999, 3, ' δ- δ+ '
5 Total synthesis of TA- TA- Bn from [2+2] cycloaddition Bn Bn Bn MM =MM Bn Sm 2 then Bz 6% MM (C) 2 DMS 3-7 to 2 o C Bn =TBDPS Bn t Bu 2 then Tf % 6 ' Bz Amine-promoted cyclocondensation -synthesis of isoxazoles- 1 CS 1 3 C rt 2 rt 9~99% stable 71~7% CS pyridine 1 =, MM, Tetrahedron Lett. 2003, 44, =,, etc. previous work fast 3 decomp. 3 =,, 62~3% yields pinacol cyclization Bn Bn Bn MM Bn 6π cyclization Sm Sm ' Bn Bn Bn Bn =sugar Bn Bn Bz Bz MM C 2 Bn Bn 1:1 mixture Bn Baran lab Group eting Bn 1) CA, aq. C 2) 2, Pd/C, 3% (2 steps) Bz C 2 Bz C 2 Bz B 3 2 Ac including separation TA- Angew. Chem. nt. Ed. 2004, 43, unstable achiral rg. Lett. 2003,, 391. chiral
6 ntramolecular aldehyde-ketone benzoin reaction 20 mol% MM MM S DBU t Bu, 40 o C Total synthesis of BE-43472B Baran lab Group eting 90%, dr=>20:1 C 2 79%, dr=>20:1 BE-43472B J. Am. Chem. Soc. 2003, 12, 432. soxazole-directed pinacol rearrangement Bn T 9% ee 3M 2 S 4 T, 40 o C Bn Bn 99%, 9% ee B mol% B 3 2, 0 o C Bn Bn, 9% ee no racemization C 2 MM C 2 94%, 60% ee Bn = 92% 9% ee 9% ee 92%, 0% ee 6% 71% ee Co Co (C) 3 (C) 3 2% ee Angew. Chem. nt. Ed. 2007, 46, 322. C 2 t Bu T, -7 o C quant. MM C 2 single isomer
7 Baran lab Group eting MM C 2 a 2 C 3, rt 3% (2 steps) Boc C Tf rt pinacol rearrangement C Boc, 0 o C S C C 2 Boc CSA reflux 9% Boc BE-43472B Angew. Chem. nt. Ed. 2013, 2, 66. egioselective C-glycosylation sugar (2 eq.) C: C : both Tf 2 : 27 : 21 Sc(Tf) 3 >9 : nd : nd T/DMPU -0 o C; Se then aq % (2 steps) / 0 o C to rt Ac CC Bn 3 (1 eq.) Bn 3 94% Ac Sc(Tf) 3 (0 mol%) Drierite, -30 o C to - o C 9% % CA-Si 2 Lewis acid (30 mol%) Drierite -30 o C to - o C 77~2% sugar sugar Angew. Chem. nt. Ed. 2014, 3, 12.
8 Baran lab Group eting Total synthesis of saptomycin B 2 2 Bn Bn 3 saptomycin B Bn DCE, -30 to o C Ac Sc(Tf) 3 (0 mol%) Drierite DCE, -30 to 2 o C Bn 3 3 Bn 3 Ac Sc(Tf) 3 (30 mol%) Drierite Bn 3 3 Bn Bn Bn Bn K 2 C 3 Ac Ac 2% saptomycin B Angew. Chem. nt. Ed. 2014, 3, Catalytic generation of arynes Tf Tf sp 3 sp Proposed mechanism Bn Tf Tf Tf t Bu 2 C fast sp 2 : favorable mol% Bn Tf slow sp 2 : unfavorable 77% Tf (catalytic) 30 mol% Tf Tf u Tf (1) u u (stoichiometric) Bn T -7 to -60 o C 2% (2) Angew. Chem. nt. Ed. 2012, 1, 336. C 2 t Bu pka ( 2 ) 24 20
9 Baran lab Group eting Total synthesis of (+)-Cinnamtannin B 1 Bn Bn =TBS Bn 93% Bn Bn Bn Bn TBS Bn not detected (less stabilized than A) Bn Bn (+)-cinnamtannin B 2 =Bn a possible precursor Model study unreactive TBS TBS DDQ (C 2 ) 2 Bn reflux 69-1% B to -20 o C Bn their strategy Bn putative biogenesis TBS Bn intermediate A TBS BS - o C Bn Bn Bn Bn Bn Bn TBS 2, Ag 2, 4Å MS, -7 to -40 o C TBS SXy Bn (1.2 eq.) Bn Bn B % Xy=2,6-xylyl Bn Bn 1 Bn 1 Bn Bn Bn SXy Bn Bn Bn =TBS =Bn 2 =TBS (+)-cinnamtannin B 2 Angew. Chem. nt. Ed. 2014, 3, 129.
TMSCl imidazole DMF. Ph Ph OTMS. Michael reaction. Michael reaction Ph R 3. epoxidation O R
eaction using diarylprolinol silyl ether derivatives as catalyst 1) C Et K C 3, ) MgBr, TF TMS hexane, 0 o C TBS p- C 6 4, T C Et 85%, 99% ee Angew. Chem., nt. Ed., 44, 41 (005). rg. Synth., 017, 94, 5.
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