Synthesis of Azadirachtin: A Long but Successful Journey
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1 ynthesis of Azadirachtin: A Long but uccessful Journey Gemma E. Veitch, Edith Beckmann, Brenda J. Burke, Alistair Boyer, arah L. Maslen, and teven V. Ley Angew. Chem. Int. Ed. 2007, Early View And Gemma E. Veitch, Edith Beckmann, Brenda J. Burke, Alistair Boyer, Carles Ayats, and teven V. Ley Current Literature Chenbo Wipf Group Aug 18th, 2007 Angew. Chem. Int. Ed. 2007, Early View Chenbo Wipf Group 1 10/29/2007
2 Azadirachtin Azadirachtin was isolated from the seed of Indian neem tree Azadirachta indica (0.2 to 0.8 percent by weight) in It acts as an antifeedant and growth disruptor against over 200 species of insect yet displays very low mammalian toxicity (LD 50 (rat) > 5g/kg). Its structure was elucidated in Commercially available: 10 Butterworth, J.. et al Chem. Commun. 1968, Kraus, W et al Tetrahedron 1987, 43, Chenbo Wipf Group 2 10/29/2007
3 Azadirachtin: tructural Features ixteen contiguous stereogenic centers, seven quaternary carbons ighly oxygenated ensitive functionalities (enol ether and epoxide) Chenbo Wipf Group 3 10/29/2007
4 Retrosynthesis Ac Me 2 C C 2 Me TB Me 2 C C 2 Me Bn Bn Me Me 2 C C 2 Me Bn Bn Me C 2 Me Bn C 2 Me Bn Me 2 C Bn Me Me 2 C Me Bn Me TE TE Me 2 C Key tranformations: C 2 Me Bn Methy acetal protection of the enol ether functionality Radical cyclization to provide the bridged ring system -alkylation followed by Claisen rearrangement to install the C8 quartenary center Chenbo Wipf Group 4 10/29/ Ms Me Bn Me
5 Preparation of Left and Fragment TB C Me + Me 1. BuLi, TMEDA, 54% 2. K, Me 2 C Me 2 i Br ime 2 60% TB C 2 Me Me Me 1. F, py, 86% 2. (CCl) 2,DM, Et 3 N, 93% 3. LiCl, DIPEA, Diethylphosphonobutyro -lactone: 95%, E:Z 5:2 Me 2 i C 2 Me Me Me 1. Tebbe reagent 2. DIPEA, ydroquinone Tol 85 o Me C, 57%, endo:exo 5:2 2 i Me 2 C Me Me 1. TA, 2 -Me, 63%, dr 7:1 Me 2 i Me 2 C 1. Piv-Cl, DMAP, py, 89% 2. NaB 4,96% Piv Piv 1. MeI, CaC 3, MeCN, 2, 100% Piv Me 2 i Me 2 C 2. DBU, 92% 3. g( 2 CCF 3 ) 2, TFA-Ac then C 3 C 3, Me 2 C 85% Kolb,. C. et al. J. Chem. oc. Perkin Trans , 2735 Chenbo Wipf Group 5 10/29/2007
6 Preparation of Left and Fragment (cont.) Piv 1. C, PPT, 94% Piv 1. TBTf, 2,6-lutidine Me 2 C 1. Dess-Martin 2. L-electride, 97% 3. ptical resolution with (-)-Camphanic acid, 40% C Me 2 C 1. Zn(B 4 ) 2 2. Li 3. C 2 N 2 79% CN 1. TBAF Me 2 C TB CN 2. TBTf, TEA 3. 3 then P 3 74% Me 2 C TB 2. NCC 2 C 2, TsCl, py 95% Me 2 C TB 2. PDC 3. LMD 85% Me 2 C DMD PPT, Me C 2 Me 1. C, PPT, 74% C 2 Me Bn Me 2 C 70%, dr 4.4:1 Me 2 C 2. BnBr, Ag 2, 61% Me 2 C 30 steps, 0.12% overall yield Chenbo Wipf Group 6 10/29/2007
7 Degradation tudy Ac Me 2 C C 2 Me 1. 2,Pd/C,76% 2. Ac 2, TEA, DMAP, 65% Ac Me 2 C C 2 Me Ac PCC, 50% Ac Me 2 C C 2 Me Ac Azadirachtin TEA, 2, 32% C 2 Me 1. C, PPT, 72% C 2 Me Bn Me 2 C 2. Ag 2, BnBr, 71% Me 2 C Ley,. V. et al Tetrahedron, 1993, 49, 1675 Chenbo Wipf Group 7 10/29/2007
8 Demethylation of the C-8 Position C 2 Me Bn 1. TsNN 2,Ts,60% Ac C 2 Me Bn 1. e 2, tbu, 60% Ac C 2 Me Bn 1. s 4,83% Me 2 C 2. C(Me) 2, PPT 3. MeNa, 79% , 2, 93% 5. Ac 2, TEA, DMAP, 92% Ac Me 2 C 2. RhCl(P 3 ) 3,70% Ac Me 2 C 2. C(Me) 2, PPT, 90% Ac Me 2 C Ac C 2 Me Bn NB, hv, 2, 50% Ac Me 2 C Ac C 2 Me Bn 2 C PCC, 84% mi 2,79% Ac Me 2 C Ac C 2 Me Bn 1. MeNa 2. (Me) 2, PPT 83% C 2 Me Bn Me 2 C Koot, W. J. et al Tetrahedron, 1995, 51, 2077 Chenbo Wipf Group 8 10/29/2007
9 Methylation of the C-8 Position 3 steps, 46% Chenbo Wipf Group 9 10/29/2007
10 Preparation of Right and Fragment 1. Bu 2 n, then MMCl, 82% py, DIPEA 3. AllylMgCl, 85% 4. BnBr, Na, 87% MM Bn 1. NB, 60% 2. Zn, N 4 Cl, 99% 3. 3, then P-P 3 4. TPAP, NM, 95% MM Bn 1. TFA, 2, 99% MM Bn Me 2 C 2. TBCl, TEA, 90% 3. C 2, NaMD, then MeI, 99% TB 1. AIBN, Bu 3 n, 70% 2. TFA, 2, 80% py, DIPEA 4. tbuk, 3 PCBr 2. Br 80% Br MM Bn Br PMB Bn 1. TMBr, 82% 2. PMBTCA, La(Tf) 3,90% 3. DIBAL- 4. Amberlyst 15, Me, 70% Br Br PMB Bn 1. MeLi, LiBr, 80% 2. iprmgbr, (C 2 ) n,80% 3. Ms 2, DIPEA, 90% Ms Me 22 steps, 4.1% Veitch, G. et al Angew. Chem. Int. Ed. Early View Chenbo Wipf Group 10 10/29/2007
11 Fragment coupling 8 steps, 17% Chenbo Wipf Group 11 10/29/2007
12 A Relay Route to Azadirachtin Ac Me 2 C C 2 Me 1. NB, Me, quant. 2. Bu 3 n, AIBN, 91% 3. BnBr, Ag 2, 60% Ac Me 2 C C 2 Me Bn Bn Me 1. DMP, 99% 2. TEA, Me, 2, 99% 3.TBTf,DIPEA,90% TB Me 2 C Azadirachtin C 2 Me Bn Bn Me 1. TBAF, quant. 2. 2,Pd/C, :99%, :80% Me 2 C C 2 Me Bn Me Amberlyst 15, 49% Chenbo Wipf Group 12 10/29/2007
13 End Game Me 2 C C 2 Me Bn Me 1. Ac 2, TEA, DMAP, 74% 2. Cl Cl Cl Cs 2 C 3,80% Ac Me 2 C C 2 Me Bn Me 1. NaB 4,CeCl 3,49% 2. 2, Pd/C, 81% Ac Me 2 C C 2 Me Me, PPT, 70% Ac Me 2 C C 2 Me DMD, 67% Ac Me 2 C Azadirachtin C 2 Me 6 steps, 11% Chenbo Wipf Group 13 10/29/2007
14 ummary The authors have demonstrated a feasible pathway for the synthesis of azadirachtin: 22 years in the making. 47 linear steps, % overall yield Key steps include a Claisen rearrangement for the formation of C8-C14 bond and a radical cyclization to form the bridged ring system. End game relies on an intermediate prepared by the degradation of the target molecule. Chenbo Wipf Group 14 10/29/2007
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