4.MeOTf,DCM,76% 5.1-B,MeCN,50 C,89% 6.Oxone,MeCN/H 2 O,0 C,67% 7.PIFA,DCM,rt; TFA/H 2 O(3/1),55 C,26%
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1 Problem Session 1 Please fill in the blank and provide each reaction mechanisms Akira Tomiyama A,i-Pr 2 Et(excess),DCM,-78 C; then1-1,dcm,-78 C,57% 2. 2,aneyi,;DMP,DCM,69% 3.TMSTf,Et 3,DCM,0to35 C; Cl,DCM,-78 Ctort,78% 1-2 =TMS =C (C Si).Tf,DCM,76% 5.1-B,C,50 C,89% 6.xone,C/ 2,0 C,67% 7.PIFA,DCM,rt; TFA/ 2 (3/1),55 C,26% 1- (C ) 2 s 1.Pd(P 3 ),ab,et,rt 2.Pb(Ac),DCE,reflux;Silicagel,DCM,rt, 56%(2steps,1:3dr) 3.TMSCl,Et 3,DCM,rt,86%.2-A,LDA,Et 2,-0 C,5% 5.S,Cs 2 C 3,C,rt 6.m-CPBA,Al 2 3,DCM,0 Ctort,60%(2steps) 2-1 C 2 TMS 7.TBAF,Ac,TF,0 Ctort,81% 8. 2-B,,-dimethylaniline, DCM, rt 9.SmI 2,TF,rt,60%(2steps) Et = Cl 2 C 2 Et 1-A 1-B 2-A 2-B Ac Ac I Ac DMP K S xone F 3 C I PIFA CF 3
2 ProblemSession1-Answer- Topic: Total syntheses by John L. Wood Akira Tomiyama Prof. John Louis Wood : B.A., Chemistry, University of Colorado :.D., rganic Chemistry, University of Pennsylvania (Prof. Amos B. Smith III) : American Cancer Society Postdoctoral Fellow, arvard University : Assistant Professor of Chemistry, Yale University : Associate Professor of Chemistry(non tenured), Yale University : Professor of Chemistry, Yale University : A. I. yers Professor of Chemistry, Colorado State University 2013-Present: obert A. Welch Distinguished Professor and Cancer Prevention esearch Institute Scholar, Baylor University 1 Total synthesis of( )-aspergilline A isolaton: from the fungus Aspergillus versicolor Zhou,M.;Miao,M.-M.;Du,G.;Li,X.-.;Shang,S.-Z.;Zhao,W.;Liu,Z.-.;Yang,G.-Y.;Che,C.-T.; u,q.-f.;gao,x.-m.rg.lett.201,16,5016. structural feature: caged hexacyclic(6/5/6/5/5/5) heterocyclic ring system six contiguous stereocenters heavily substituted tetramic acid bioactivity: against tobacco mosaic virus against several human cancer cell lines Gao,X.-M.etal.rg.Lett.201,16,5016. total synthesis: akhla,m.c.;wood,j.l.j.am.chem.soc.2017,139,1850(problem1) Aspergilline A A,i-Pr 2 Et(excess),DCM,-78 C; then1-1,dcm,-78 C,57% 2. 2,aneyi,;DMP,DCM,69% 3.TMSTf,Et 3,DCM,0to35 C; Cl,DCM,-78 Ctort,78% Cl 1-2 =TMS =C 2 1-A Cl Cl Et(i-Pr) 2 Et(i-Pr) 2 1-A 1-5 Et(i-Pr) 2 (i-pr) 2 Et
3 1-7 Et(i-Pr) 2 BMD Et(i-Pr) BMD BMD BMD Et(i-Pr) aney i BMD BMD Ac Ac I Ac Ac Ac Ac I Ac Ac I Ac Ac I BMD TMS Tf Et 3 TMSTf Et 3 Discussion 1 BMD TMS Cl BMD Cl Discussion 1 Cyclization goes after -TMSwasreplasedto-Cl =TMS =C 2
4 Discussion 1-1: egioselectivity of silylation and stereoselectivity of cyclization sp 2 (smaller) BMD BMD Cl 3 BMD Cl 3 TMSTf S Et 3 L or ;Cl sp 3 (larger) M L 1-17 (trans-enolate) major minor ( Lewisbasicityofamide-ishigherthanthatofester-.) 1-18La 1-19 boat form (favored) Si 1-2 =TMS =C L 1-18Lb 1-20 half-chair form (disfavored) Si Lc 1-22 boat form (favored) Si Ld 1-2 half-chair form (disfavored) Si C C boat form(favored) C 2 C half-chair form(disfavored)
5 1-18a 1-18b boat form (favored) =TMS =C Si Si Si Si half-chair form (disfavored) 1-18c 1-18d half-chair form (disfavored) boat form (favored) =TMS =C 2 Before revision DDQ Cl Cl C C Cl Cl C C
6 Cl Cl DDQ SET C C Cl Cl C C 1-27 Cl Cl C C Cl Cl C C Tf,DCM,76% 5.1-B,C,50 C,89% 6.xone,C/ 2,0 C,67% 7.PIFA,DCM,rt; TFA/ 2 (3/1),55 C,26% 1- (C ) 1-3 (C Si) =TMS =C 2 1-B K S xone F 3 C I PIFA CF 3 Tf Tf B
7 Possible reaction mechanisms 1-30a 1-35 (u:d=3:2) emming,k.etal. Tetrahedron Lett. 2008, 9, b negative charge on electron-rich carbon o problem ( Inductive effect of- can stabilize the carbanion.) 1-30c SET X 1 2 X 1 =,Et, 2 =, X=Et, 2,S Matsumoto,K.etal.Bull.Chem.Soc.Jpn.1983,56, n SEt EtS n n=1,2,3 emming, K. et al. Tetrahedron Lett. 2008, 9, S xone S
8 S S K concave TMS 2 convex ' TMS Before revision TMS F 3 C I CF 3 TMS Thisadditionmayalsobenot PIFA occurred because of steric repulsion. CF 3 I F 3 C CF 3 I rbits are hard to interact. I TMS CF 3 CF 3 C TMS 1-6 CCF3 TMS TMS + + epimerization
9 TMS TMS 1-3 F 3 C I CF 3 PIFA I CF I TMS CF 3 CF 3 C TMS TFA, 2 TMS (C ) =C 2 5steps Aspergilline A 2 Total synthesis of( )-phomoidride D isolaton: from a nonsporulating fungus ATCC 7256 Spencer, P.; Agnelli, F.; Sulikowski, G. A. rg. Lett. 2001, 3, 13. structural feature: [.3.1] bicyclo system containing a bridgehead double bond four contiguous stereocenters maleic anhydride moiety bioactivity: not reported omoidride D total synthesis: Leung,J.C.;Bedermann,A.A.;jardarson,J.T.;Spiegel,D.A.;Murphy,G.K.;ama,.;Twenter,B.M.; Dong, P.; Shirahata, T.; McDonald, I. M.; Inoue, M.; Taniguchi,.; McMahon, T. C.; Schneider, C. M.; Tao,.; Stoltz, B. M.; Wood, J. Angew. Chem. doi: /ange (problem 2) -8-
10 s 1.Pd(P 3 ),ab,et,rt 2.Pb(Ac),DCE,reflux; Silica gel, DCM, rt, 56%(2steps,1:3dr) 3.TMSCl,Et 3,DCM,rt,86%.2-A,LDA,Et 2,-0 C,5% 5.S,Cs 2 C 3,C,rt 6.m-CPBA,Al 2 3,DCM, Ctort,60%(2steps) 2-2 C 2 TMS 2 C 2 2-A Pd 0 (P 3 ) s s reductive elimination Tsuji-Trost reaction oxidative adittion 2-1 Pd II s Pd II transmetalation 2- ab 3 s ab s s Pb IV (Ac) 3 Ac Pb IV (Ac) ' Before revision s Ac Pb IV Ac Ac s Pb II (Ac)
11 Before revision s s Ac Ac Ac Ac Ac 2-9' These carbons should locate onthesameplaneas each quinone. Ac 2-9'' s s Ac 2-10a' Ac 2-10b' s s 2-10a'' favor 2-10b'' disfavor silica gel silica gel s s Ac rbits are hard to interact. Ac 2-11a 2-11b Ac Ac s s against edt's rule difficult a 2-12b -10-
12 s Pb IV (Ac) 3 Ac 2-7' Pb IV (Ac) s s Ac Ac Pb IV Ac Ac Pb IV 2-8' 2-8'' Pb II (Ac) 2 Pb II (Ac) 2 s s Ac Ac 2-10a 2-10b s s Ac 2-10a' Ac 2-10b' s s 2-10a'' favor b'' disfavor
13 silica gel silica gel s s Ac 2 2 Ac 2-11a 2-11b 2 2 s s 2-13a 2-13b Ac Ac s s 2-1a 2-1b major product (dr=3:1) minor product s TMS Cl TMSCl sp 2 carbon sp 3 carbon s Li TMS 2 2 LDA 2 2-A 2-1a 2-15 Li -12-
14 S S 2 C 2 TMS S S S 2 C 2 TMS S Cl 2 C 2 TMS m-cpba 2 C 2 TMS C 2 TMS 2-2 C 2 TMS 7.TBAF,Ac,TF,0 Ctort,81% 8. 2-B,,-dimethylaniline, DCM, rt 9.SmI 2,TF,rt,60%(2steps) 2-B 2-2 Et 2-3 Et -13-
15 C 2 TMS + C 2 TMS TBAF + F Et 2-B Et 2-B2 2-B Et 2 Et Sm II I Sm II I 2 SmI 2 SET Discussion 2 Et Et Et 5-exo-trig Et 5-exo-tet
16 Et 10 steps 2-3 omoidride D Discussion 2: adical cascade cyclization promoted by single electron transfer low reduction potential electron deficient Sm II I 2 fast slow Sm II I 2 Et PathA PathB 2-2 Et 2-25AB electron rich high reduction potential fast slow Et Sm II I 2 Et Procter,D.J.etal.rg.Lett.2003,5, _PS_iroaki_Matoba 2-25CD 2-26CD Et PathC PathD 2-27CD SmI 2 TF/ 0 C,9% Cyclopropane ring was not opened. Unsaturated lactone was reducted. Procter,D.J.etal.rg.Lett.2003,5,
17 PathA Sm II I 2 5-endo-trig disfavored Et Et (Baldwin's rule) But 5-endo-trig often precedes -exo-trig. 2-26A 2-25AB Gimisis,T.etal.J.Am.Chem.Soc.2002,12, exo-tet Et 2-28A work-up 2-3 Et Et PathB Sm III I Sm II 2 I 2 Et -exo-trig Et high angle strain Et unconjugated 1 radical 2-27B 2-25AB 2-26B o problem(adical reactions are usually kinetic control.) work-up Et 6-exo-tet Et 2-28B A PathC Sm III I 2 5-exo-trig 5-exo-tet fast Et Et 2-27CD 2-28C Et 2-3 PathD 6-exo-tet -exo-trig Et Et slow high angle strain 2-27CD D Et 2-29
Problem session (3) Daiki Kuwana. Please fill in the blank and explain reaction mechanisms and stereoselectivities.
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Radical Reactions. Radical Stability!!! bond dissociation energies X Y X + Y. bond BDE (kcal/mol) bond BDE (kcal/mol) CH 3 CH 3 CH 2 95 O H R 2 C H
adical eactions adical Stability!!! bond dissociation energies X Y X Y bond BDE (kcal/mol) bond BDE (kcal/mol) C 3 104 108 C 3 C 2 98 110 95 2 C 102 (-) 93 (C-) 92 C 3 C 3 36 89 85 C 3 C 3 80 adical eactions
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