AB9-13![]()
1-8![]()
14-17![]()
NHBrNHNOONBocONHBrOSiOTIPSHNHOSiOTIPSNHNOONBocNHBrClClNHN+OO-SOONHNsONNHNBrNMeClClNNHNBrNMeClClPOOOPhOOPhNN+N-N3NHBrNN+N-N3![]()
BrNOONHBrNN+N-N3Br![]()
NHBrNN+N-N3BrOHH![]()
BrNOONBrNN+N-N3BrOHBrHH![]()
OON![]()
NHBrNN+N-N3BrOH![]()
NHBrNN+N-N3BrONHBrNN+N-N3BrOB:NBrNN+N-N3ONHOSiOTIPSNHNOOSiOTIPSNN+N-N3![]()
NOSiOTIPSNHNN+N-N3ONOSiOTIPSNHNN+N-N3ONOSiOTIPSNHNH2O![]()
NOSiOTIPSNHONH![]()
NHOSiOTIPSNHONHTotal Synthesis of (±)-Perophoramide
Fuchs, J. R.; Funk, R. L.*
J. Am. Chem. Soc. 2004, 126, 50681) (COCl)2, MeOH, Et2O, 0 ºC
2) BH3•SMe2, THF, reflux
3) PPh3, I2, imidazole
4) NaN3, DMF, 50 ºC
5) NBS (2 equiv.), THF, t-BuOH, H2O
6) 1, Cs2CO3
7) NaH, Boc2O
8) PPh3, THF, H2O, 50 ºC9) NCS, AcOH
10) NaHMDS, NsCl
11) TBAF
12) DPPA, DIAD, PPh3
13) PMe3, THF1(±)-Perophoramide15) Hint: Boc falls out in this step14) MeI, Cs2CO3, MeCN
15) Meerwein’s salt, DIPEA
16) PhSH, Cs2CO3, DMF, 45 °C
17) MnO2, CH2Cl2(±)-Perophoramide2) Hint: complete reduction of the side chain
3) Name of the reaction?
Appel reaction
5) Provide a mechanism
hint: an oxindole is finally formed
6) How would you prepare 1?
Hint: a cycloaddition followed by ring opening
8) Name of the reaction?
Staudinger reduction
Hint: Two new rings form in this cascade10) Hint: mono-nosylationDPPA13) A new ring formsMechanism of Step 5: Oxindole formationMechanism of Step 6: Diels-Alder/ring opening cascadeMechanism of Step 8: Staudinger/transamidation cascade![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()
![]()