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AONMeOOHMeMeHHMeMeOOOBrOOEtBrOOMeMgClMgClNNt-But-But-But-BuOOCoClN+OOMeO-BrOOEtIMeONOONBocMeMeOSiOTBSOMeMeOOOEtOHHOOOOAcMeHMeMeOOAcOOOEtAsymmetric Total Synthesis of Norzoanthamine
Zhengyuan Xin, Hui Wang, Haibing He, Xiaoli Zhao, Shuanhu Gao
Angew. Chem. Int. Ed. 2021, 60, 12807-12812.1. NaOH, H2O2, MeOH then
N-acetyl-L-cysteine, (PhSe)2, NaOH, MeOH
2. imH, DMAP, TBSCl, DMF
3. DBU, HCHO (aq.), THF
4. O3, -78 °C, MeOH then Cu(BF4)2, Fe(BF4)2, -20 °C
5. TESCl, imH, DMAP, DMF
6. P(n-Bu)3, HCHO (aq.), CHCl3
7. TIPSCl, imH, DMAP, DCM
8. MeLi, Et2O, -78 °C
9. PDC, 4Å MS, MeCN/PhMe, 65 °C
10. PPTS, MeOH
11. PhNMe2, DCM, 1
12. AIBN, Bu3SnH, PhMe, reflux
13. Ph3PCH3Br, t-BuOK, 0 °C
14. TBAF, THF
15. p-TSA, EtOH, CHCl3
16. DMP, DCMBName centered and bold17. 2, THF, -78 °C to r.t.
18. Ac2O, Et3N, DMAP, DCM
19. 3, PhSiH3, acetone, 38 °C then TBAF, NaOH (aq.)
20. Na, NH3, -78 °C
21. Ac2O, DMAP, THF then (CO2H) (aq.)
22. Mn(dpm)3, PhSiH3, t-BuOOH, i-PrOH then IBX
23. Et3N, TMSOTf, DCM, -78 °C to -20 °C then IBX, 424. CSA, H2O, MeCN
25. MeLi, THF then LiAlH4 then TIPSOTf, imH, THF/MeCN
26. TEMPO, PIDA, DCM
27. t-BuLi, 5, THF then SM then (CO2H)2
28. t-BuLi, 6, THF/Et2O, -78 °C then SM
29. TPAP, NMO, 4Å MS, DCM
30. Pd(PPh3)4, Bu3SnH, THF
31. TBAF, THF, 55 °C
32. PCC, NaOAc, 4Å MS, DCM
33. 2-methyl-2-butene, NaClO2, NaH2PO4, t-BuOH, THF, H2O
34. AcOH, H2O, 100 °CStep 1: Name of the SM?Step 6: Name of the reaction?Step 9: Name of the reaction?Hint: Step 15 is an epimerizationStep 12: Name of the reaction?Step 29: Name of the reaction?
Hint: Three reactions take placeStep 33: Name of the reaction?
Why is 2-methyl-2-butene added?Step 20: Name of the reaction?Hint: Two transformations occur in step 32123456What is the general name of the ligand in complex 3, how are these ligands made?Hint: Step 10 is a mono deprotectionHint: Step 14 is a mono deprotectionHint: Step 25 mono deprotection happens(S)-+-carvoneBaylis-HillmanBabler oxidationUeno-Stork cyclizationBirch reductionLey-Griffith oxidationPinnick oxidation. Scavenging hypochlorous acid byproductSalen. Condensation of salicylaldehyde derivatives + ethylenediamine derivatives![]()
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