Prof. Ang Li. Literature Seminar Kosuke Minagawa (D2)

Transcription

1 Prof. Ang Li Literature Seminar Kosuke Minagawa (D2) 1

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4 aspidodasycarpine 1) 2 C sespenine 3) atural Products Synthesized by Ang Li group clostrubin 6) drimentine A 7) i-bu rubriflordilactone A 4) delavatine A 8) C fusarisetin A 2) daphenylline 5) ileabethoxazole 9) 1. J. Am. Chem. Soc.2016, 138,3982.; 2. J. Am. Chem.Soc. 2012, 134,920.; 3. Angew. Chem. Int. Ed. 2014, 53,9012.; 4. J. Am. Chem. Soc. 2014, 136, ; 5. ature Chem. 2013, 5, 679.; 6. ature commun. 2015, 6, 6445.; 4 7. J. Am. Chem. Soc.2016, 138,3982.; 8. J. Am. Chem. Soc. 2017, 139,5558.; 9. Angew. Chem. Int. Ed.2016, 55,2851.

5 ~ 6 -Electrocyclization/ Aromatization ~ Tf C C 2 Si i-pr i-pr TBS h (g lamp) 0 C 71% Bu 3 Sn Pd(PPh3 ) 4 55% Ph 86% TIPS S 2 Et Li(TMS) 2 C 2 DBU, air, 60 C 67% TBS TBS Lu,Z.;Li,Y.;Deng,J.;Li,A. ature Chem. 2013, 5,679. TIPS mesitylene 140 C, air 68% Sii-Pr 2 Sii-Pr 2 Yang,M.;Yang,X.;Sun,.;Li,A. Angew. Chem. Int. Ed. 2016, 55,2851. toluene, 90 C; DDQ 82% 5 Li,.;Chen,Q.;Lu,Z.;Li,A. J. Am. Chem. Soc. 2016, 138, C 2 TIPS

6 Br C 2 + Entry Conditions Yield Conditions AIB,n-Bu 3 Sn, toluene, 80 C Et 3 B, 2,n-Bu 3 Sn, TF, 22 C [Ru(bpy) 3 ]Cl 2 6 2, Et 3, blue LED, DMF, 22 C [Ir(bpy) 2 (dtbbpy)]pf 6, Et 3, blue LED, DMF, 22 C 8% 13% 11% 90% C 2 87% (d.r. = 2.2:1) C 2 C 2 81% 73% (d.r. = 5.8:1) 6 Zhou, S.; Zhang, D.; Sun, Y.; Li, R.; Zhang, W.; Li, A. Adv. Synth. Catal. 2014, 356, 2867.

7 R R 2 Eu(fod) 3 (10 mol%) 1,2-dichloroethane 80 C,24 h R 1 R 2 X 90% X =Br (82%) X =(87%) TBS C 2 91% (d.r.=1:1) 81% (d.r.=1.6:1) 7 Xiong,X.;Zhang,D.;Li,J.;Sun,Y.;Zhou,S.;Yang,M.;Shao,.;Li,A. Chem. Asian J.2015, 10,869.

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10 aspidodasycarpine R R 2 indole cyclization R 1 R 2 2 R 1 3 Au(I) Toste cyclization R Li, Y.; Zhu, S.; Li, J.; Li, A. J. Am. Chem. Soc. 2016, 138, 3982.

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12 1) DDQ, TF/ 2 =10/1 88% 2) scl, Et 3 DMAP,C 2 Cl 2 73% s TIPSTf, Et 3 C 2 Cl 2,95% s (p-cf 3 Ph) 3 PAuCl, AgSbF 6,TTBP 4A MS,86% s t-bu TIPS t-bu t-bu TTBP (2,4,6-tributylpyrimidine) 12 Li,Y.;Zhu,S.;Li,J.;Li,A. J. Am. Chem. Soc. 2016, 138,3982.

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14 s TMSC BF Et 2, 76% s DIBAL C 2 Cl 2, -78 o C s C ab 4 /C 2 Cl 2 0 o C, 90% aq. C a 2 C 3 /C 2 Cl 2 54% (2 steps) s s 14 Li, Y.; Zhu, S.; Li, J.; Li, A. J. Am. Chem. Soc. 2016, 138, 3982.

15 Synthesis of the lactol s Ph F 3 C Bn (Yamada-Yu rgt.) s 1,4-dioxane 4Å MS,Tf Bn Bn Basic condition: retro-aldol Cl 3 C selfinstability against acid promoters. Bn Bn Bn I Bn 15 Li,Y.;Zhu,S.;Li,J.;Li,A. J. Am. Chem. Soc.2016, 138,3982.

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17 Divergent Synthesis from Common lactol Bn C 2 aspidodasycarpine lonicerine Ph lanciferine (proposed) 17 Li,Y.;Zhu,S.;Li,J.;Li,A. J. Am. Chem. Soc. 2016, 138,3982.

18 ab 4, 0 o C Bn aspidodasycarpine 1) BBr 3, -78 o C, 78% 2) a naphthalenide -78 o C, 76% Bn Bn 1) AZAD acl 2 2) TMSC 2, 0 o C, 80% (2 steps) Bn 90% a 18 Li,Y.;Zhu,S.;Li,J.;Li,A. J. Am. Chem. Soc. 2016, 138,3982.

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20 TPAP, M C 2 Cl 2, 0 o C, 86% aq. Li TF, 94% Bn Bn Bn 1) AZAD acl 2 Bn (X-ray crystallographic analysis) a 2 C 3, 79% Bn I 2) I 2, ac 3 C, 0 o C 91% (2 steps) Bn 20 Li,Y.;Zhu,S.;Li,J.;Li,A. J. Am. Chem. Soc. 2016, 138,3982.

21 Completion of the Synthesis of lanciferine 1) a naphthalenide 2) C 2, 2, Pd/C, 50% (2 steps) cinnamic anhydride DMAP, pyridine 79% 18 Ph Bn lanciferine (proposed) Ang Li et al. synthesized lanciferine (proposed), but 1 MRchemical shiftof C18 methyl drastically differed fromreported ( = 0.2). (Lewin, G.; Kunesch,.; Posson, J. J. Indian Chem. Soc. 1978, 55, 1096.) Li,Y.;Zhu,S.;Li,J.;Li,A. J. Am. Chem. Soc. 2016, ,3982.

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23 Daphniphyllum alkaloids daphnilactone A eathcock,1989 a daphenylline Li,2013 d Yokoshima&Fukuyama,2016 e C 2 Ac daphmanidin E Carreira,2011 b longeracinphyllin A Li,2017 e codaphniphylline eathcock,1995 c a ethcock,c.. et al. J. Am. Chem. Soc. 1989, 111,1530. b Carreira,E.M. et al. Angew. Chem. Int. Ed. 2011, 50, c ethcock,c.. et al. J. rg. Chem. 1995, 60,1120. d Li,A. et al. at. Chem. 2013, 5,679. e Yokoshima,S.;Fukuyama,T. et al. Angew. Chem. Int. Ed. 2016, 55,6067. e Li,A. et al.di: /jacs.7b

24 C 2 [3+2] C 2 longeracinphyllin A s C 2 2 C TBS C 2 I 24 Li, J.; Zhang, W.; Zhangm F.; Li, A. DI: /jacs.7b09186

25 1) s TBDPS s conditions Entry s Conditions + 6-exo s Yield 7-endo DIAD, PPh 3, TF 1 a Au(PPh 3 )Tf 2 66% 0% 2) TBDPSTf 85% (2 steps) 2 b 3 b,c AgTf 2 AgTf 2,Ph 3 P 15% 20% 8% 7% 4 b,c,d AgTf 2,Ph 3 P,TTBP, 4Å MS 74% 25% 99%ee 5 b,c,d AgTf 2,CyJohnPhos, TTBP, 4ÅMS 84% a 5mol%[Au], /toluene (1/10), 22 o C,30 min. b 6mol%[Ag],i-Pr/C 2 Cl 2 (1/20), 22 o C, 24 h. c 5mol%[Phosphineligand]. t-bu d 10 mol%ttbp, 10 wt%4å MS. 5% PCy2 t-bu t-bu TTBP CyJohnPhos 25 Li, J.; Zhang, W.; Zhangm F.; Li, A. DI: /jacs.7b09186

26 s 1) p-thiocresol DMF, K 2 C 3 2) 2 C C 2 EDCI, BT, Et 3, C 2 Cl 2 TBS 2 C TBS 3) DBU,C 95 o C C 2 TBS rt to95 o C 69% (3 steps) C 2 Zn, CuI sonication 35 o C, 90% C 2 I 1) F py, TF 0 o Cto rt 2) I 2, imidazole PPh 3, C 2 Cl 2 0 o C, 85% (2steps) C 2 TBS 26 Li, J.; Zhang, W.; Zhangm F.; Li, A. DI: /jacs.7b09186

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30 S Lawesson's reagent 1,2-dichlorobenzene 170 o C S Silica gel air, 67% S Raney i Et, 90% longeracinphyllin A 30 Li, J.; Zhang, W.; Zhangm F.; Li, A. DI: /jacs.7b09186

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36 phosphine-catalized [3+2] reaction is generally known stepwise mechanism. - In the first step, necleophile attacks to less hindered carbon from convex face. PAr 3 C 2 C 2 PAr 3 PAr 3 C 2 C 2 C 2 C 2 C 2 PAr 3 C 2 C 2 36

37 -the dienophile reacts from concave face, because of the steric repulsion between phosphine legand and highlighted and/or? Ar 3 P Ar 3 P C 2 C 2 Ar 3 P C 2 C 2 C 2 37

38 chanism of the photocatalyzed rafical conjugate addition 38