Studies toward the Synthesis of Azadirachtin: Total Synthesis of a Fully Functionalized ABC Framework and Coupling with a Norbornene Domain
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1 Studies toward the Synthesis of Azadirachtin: Total Synthesis of a Fully Functionalized ABC Framework and Coupling with a Norbornene Domain Nicolaou and Co-workers Angew. Chem. Int. Ed. 2005, 44, 3443 C 2 Me Ac Me 2 C David Wipf Group 1 9/4/2005
2 Azadirachtin: Structural Mystery for 20 years -Isolated in 1968 from Azadirachta indica, the indian Neem tree, with no structure proposed. -Controversial structure proposed in 1975 by Nakanishi. Me 2 C Ac Me 2 C -In 1987, Kraus and Co-workers published the accepted structure Structure C 2 Me Ac Me 2 C Revised Structure -Azadirachtin is a potent insect anti-feedant, as well as growth inhibitor. -It is non-toxic, biodegradable, and "natural", and therefore an attractive pesticide. -Azadirachtin is unstable to mild acidic, basic and photolytic conditions. -Its biological mode of action is unknown. 16 contiguous chiral centers 7 tetrasubstitued carbons 7 rings Extremely dense oxygenation -Given is limited availability, simpler analogs are often targeted in hopes of maintaing effectiveness in the field. -Several groups have investigated its total synthesis. J. Chem. Soc. Chem. Commun. 1968, 23. J. Am. Chem. Soc. 1975, 97, Tetrahedron 1987, 43, 2779 David Wipf Group 2 9/4/2005
3 Some ther Approaches to Azadirachtin C 2 Me Shibasaki and Co-workers Ac Me 2 C 28 Steps TBDMS 3 steps from (-)-ethyl lactate R C 2 Me R TBDMS [] (-)-Azadirachtin R Me 2 C M Mori and Co-workers J. rg. Chem. 1989, 54, Steps TBS C 2 Me SePh Bu 3 Sn AIBN 28% TBS C 2 Me 12 Steps TBS Me Tetrahedron Lett. 1997, 38, 4429 Tetrahedron 1996, 52, David Wipf Group 3 9/4/2005
4 Ley and Co-workers Claisen-Radical Cyclization Approach C 2 Me Me 2 C C 2 Me Bn Me PMB MWI (15 x 1 min) o-dcb 180 C 88% Me 2 C C 2 Me Bn Me -All Lewis acid catalysis failed. PMB Ac Me 2 C 1) TESTf 2) DDQ 3) Na, CS 2, MeI TES Me 2 C C 2 Me Bn Me Bu 3 Sn AIBN 81% TES Me 2 C C 2 Me Bn Me S SMe TES Me 2 C C 2 Me Bn. Me TES Me 2 C C 2 Me Bn. Me rg. Lett. 2002, 4, 3847 Sterically Unprotonatable? David Wipf Group 4 9/4/2005
5 An Ireland-Claisen Approach C 2 Me Murai and Co-workers Ac Me 2 C C + Me DEIPS EDCI, DMAP 72% Me DEIPS Me DEIPS C 2 LMDS Me 2 SiCl 2 Toluene rg. Lett. 2002, 4, % dr: 4:1 -System lacks functionalization on decalin system. David Wipf Group 5 9/4/2005
6 Construction of the decalin system: Installation of dense oxygenation Ac Me 2 C C 2 Me 1) SEMCl (85%) 2) Li, N 3 (80%) SEM 1) NaB 4 (99%) 2) TBDPSCl (80%) 3) PPTs TBDPS SEM SEM 1) Comins' Reagent (72%, 2 stps) 2)Pd(Ac) 2, PPh 3 C, Me (89%) TBDPS C 2 Me 1) DIBAL (95%) 2)B 3, 2 2 (65%) SEM TBDPS ACIE, 2003, 42, ) Na, BnBr 2) TBAF (91%, 2 stps) 3) Swern (89%) SEM Bn Bn 1) KMDS, TESCl SEM Bn Bn 2) PhSeCl 3) % over three steps 1) LMDS, NCC 2 Me (93%) 2) Yb(Tf) 3, C 2 3) TBSTf (74%, 2 stps) 4) TBP, triton B (87%) SEM Me 2 C Bn TBS Bn David Wipf Group 6 9/4/2005
7 Final manipulation of the decalin system C 2 Me Ac Me 2 C SEM Bn Bn Me 2 C TBS 1) TBAF SEM Bn 1) (PhSe) 2, NaB 4 (91%) Bn 2) NaB 4 (63%) 2) Ac 2 (92%, 2 stps) Me 2 C 3) TBS 2, Pd/C (98%) 4) TESCl (82%) SEM TES Ac Ac Me 2 C Ac 1) DMP (91%) SEM Ac 1) NaCl 2 Ac 2) Ph 3 PC 2 (80%) 3) cat. DDQ (97%) 4) DMP (92%) Ac Me 2 C Ac 2) 0.5 M Cl (94%, 2 stps) 3) Se 2, TBP (51%) Ac Me 2 C Ac Decalin Partner David Wipf Group 7 9/4/2005
8 Temporary Linkage and Radical Cyclization C 2 Me Ac Ac Me 2 C Ac Me 2 C Ac + Me PMB Ac Ac Me 2 C Ac Br Br 2 80% Ac + PMB Ac Me 2 C ~1:1 Br Ac Me PMB + Me Br PMB xonium Intermediate TTMS, AIBN 80% TTMS, AIBN 80% Ac Ac Ac Me 2 C Ac Me Ac Ac Me 2 C Ac PMB Me Ac Me 2 C Ac. PMB Me Radical Cyclization Pathway 5-exo-trig cyclization followed by 1,5- shift and PMB loss 5-exo-trig cyclization followed by intermolecular quench -Cyclization extremely substrate dependant! David Wipf Group 8 9/4/2005
9 Towards Azadirachtin: xidative opening of the Acetal Linkage Ac Me 2 C C 2 Me Ac PMB 1) 2, Pd() 2 Ac Bz Ac Me 2 C Ac Me 2) BzCl Ac Me 2 C Ac Me TFA Ac Ac Me 2 C Ac Bz PCC 80% Ac Ac Me 2 C Ac Bz 75% over three steps David Wipf Group 9 9/4/2005
10 Conclusions C 2 Me Ac Me 2 C -A fully oxygenated decalin system was prepared and coupled to a model bicycle. -Radical cyclization and subsequent cleavage of the oxo-linkage provides high-yielding access to the sterically congested C8-C14 bond of Azadirachtin. -Bicycle lacks functionalization -Route to decalin partner is 32+ steps, often falling into protecting group traps, a consequence of the dense oxygenation. Ac Me Ac Me 2 C Ac PMB Decalin Partner Model Bicycle Ac PMB Ac Ac Me 2 C Ac Me Ac Me 2 C Ac Bz David Wipf Group 10 9/4/2005
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