A Review of Total Synthesis of Spirotryprostatin A and B. Jinglong Chen Supergroup meeting Princeton University June
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1 A Review of Total Synthesis of Spirotryprostatin A and B Jinglong Chen Supergroup meeting Princeton University June
2 ovel Mammalian Cell Cycle Inhibitors, Spirotryprostatins A and B Me Spirotryprostatin A Spirotryprostatin B Isolated from the fermentation broth of Aspergillus fumigatus BM939 in 1996 by sada et al. Both compounds inhibit the mammalian cell cycle in the G2/M phase Spirotryprostatin B shows cytotoxic activity on the growth of human leukemia cell line sada. J. Antibiot. 1996,49,832 sada. Tetrahedron 1996, 52, 12651
3 Structure features Me Me Spirotryprostatin A Me Spirotryprostatin B L-Triptophan 2 A unique spiro-fusion to a pyrrolidine (dihydro-pyrrole) at the 3-position of the oxindole The annulated diketopiperazine ring A prenyl appenage and it s relative stereochemistry with spiro linkage L-Proline Senecialdehyde
4 Me Key Players xidative spirorearrangement of an indole ----Samuel J. Danishefsky, Spirotryprostatin A ----A. Ganesan, Spirotryprostatin B Mannich reaction on an oxindole ---- Samuel J. Danishefsky, Spirotryprostatin B Stereoselective [1,3]-dipolar cycloaddition ----Robert M. Williams, Spirotryprostatin A and B Asymmetric heck cyclization ----Larry E. verman, Spirotryprostatin B Asymmetric nitroolefination ----Kaoru Fuji, Spirotryprostatin B Stereoselective intramolecular -acyliminium ion spirocyclization ----David A. orne, Spirotryprostatin A and B MgI 2 -catalyzed ring-expansion reaction ----Erick M. Carreira, Spirotryprostatin B
5 Me Danishefsky s Synthesis of Spirotryprostatin A 6-methoxytryptophan Me X Y R xidation Me L R Tetrahydro-ß-carboline Install double bond Me R X Y Spirotryprostatin A Spiropyrrolidine-3,3 -oxindole Danishefsky S. J. et al ACIEE 1998, 37, 1138 Danishefsky S. J. et al JACS 1999, 121, 2147
6 Me Pictet-Spengler Reaction and xidative Rearrangement Build Spiropyrrolidine-3,3 -oxindole S C 2 Me C 2 Me Me 2 a Me 18 S b Me Boc S Me cis:trans = 2:1 c C 2 Me d Boc C 2 Me Br C 2 Me Boc Me S Me S Me S a) C 2 Cl 2, CF 3 C 2,molecular sieves (4 Å), 0 C-20 C, 88%; b) Boc 2, C 3 C, Et 3,,84%;c) BS, TF, 2, Ac, 46%;d) CF 3 C 2, C 2 Cl 2, 93%.
7 Me Formation of Diketopiperazine Ring and Complete the Synthesis Me S C 2 Me Troc Cl a Me S b Me S c Me d Me Spirotryprostatin A a) C 2 Cl 2, Et 3 ; Zn, 4 Cl, 2, TF, Me, 68%; b) ai 4, 2, Me; c) C 3,, 80% over two steps; d) RhCl 3 3 2, Et,, 41%. Troc:2,2,2-trichloroethoxycarbonyl.
8 Me Danishefsky s Synthesis of Spirotryprostatin B 8 9 Base D Me Me Me 2 X C Pictet-Spengler Cyclization X C 2 Me x? 18 x Danishefsky S. J. et al ACIEE 2000, 39, 2175
9 Me Formation of Spiropyrrolidine-3,3 -oxindole by Mannich Reaction C 2 C 3 2 Cl a C 2 C 3 2 Cl b C C 2 C 3 3 S 18 S C 2 C 3 Boc Boc c C 2 R R C 2 C 3 R R C 2 C 3 S R C 2 C 3 3-epi 3-epi-18-epi 18-epi a) equiv DMS, 6 equiv 12 Cl, Ac, [5 mol% ],25 C, 4 h (95%); b). Et 3, MS 3 Å, pyridine, 0 C to RT, 9 h; c). 1.2 equiv BP-Cl, C 2 Cl 2, 2.5 equiv Et 3, 0 C to 25 C, 2 d, (90%)
10 Me Danishefsky s Synthesis of Spirotryprostatin B C 2 C 3 Boc (1) 2.2 equiv LiMDS TF, 0 C, 30 min (2) 2.2 equiv SeCl TF, 0 C, 2 h Se C 2 C 3 Boc (3) 4 equiv DMD TF, 0 C, 4 h R 3-epi R R C 2 C 3 R 18-epi Boc C 2 C 3 78% Boc 48% C 2 C 3 (1) TFA/C 2 Cl 2 (1/5) 25 C, 30 min (2) (C 2 5 ) 3, C 2 Cl 2 25 C, 4 h Boc 6% 86% 81% R s s spirotryprostatin B 5 steps (7%) s R R 3-epi-spirotryprostatin B 5 steps (7%) s s 18-epi-spirotryprostatin B 5 steps (1%)
11 Me Ganesan s Synthesis of Spirotryprostatin B ---Amazing effect of Proline C 2 C 3 2 C(Me) 3 C C 2 C 3 Fmoc-L-Pro-Cl Pyridine, C 2 Cl 2 46% 2 steps C 2 C 3 Fmoc 68% BS, TF-Ac- 2 Spirotryprostatin B 2% and Byproducts 1. LDA, -78 C 2. SeBr, -75 C 18 20% piperidine in C 2 Cl 2 100% C 2 C 3 Fmoc Ganesan A. et al JC 2000, 65, 4685
12 Me Williams Synthesis of Spirotryprostatin B X R 4 2 C R 3 R 2 CR 1 [1,3] dipolar C 2 C 2 R 4 C 2 R 5 Spirotryprostatin B X C 2 R 4 Williams R. M. et al JACS 2000, 122, 5666 Williams R. M. et al Tetrahedron 2002, 58, 6311
13 Me Asymmetric [1,3] Dipolar Cycloaddition Build the Spiropyrrolidine-3,3 -oxindole Core Diphenylmorpholinone Me C 2 Et Me C 2 Et C Me Me Me Toluene, MS 82% Isovaleraldehyde Et 2 C xindolylideneacetate
14 Me Williams Synthesis of Spirotryprostatin B Me C 2 Et 2, PdCl 2 TF, Et 60 psi, 36h 99% Me C 2 Et 1. D-pro-Bn, BP, Et 3, MeC (74%) Me 2. 2, Pd-C,Et 3. BP,Et 3,MeC 94% (2 steps) C 2 Et 1. DCC, DMAP S BrCCl 3, eat 34-43% 2. ame,me C 2 LiI, py., reflux 70-74% Ts Toluene 89% C 2 Et Spirotryprostatin B
15 Me Williams Synthesis of Spirotryprostatin A Me TMS TFA Toluene 0 C Me C Me Me Me Toluene, MS 3A Me 20% Me nprc, Ac, 65 C Me 2, Pd() 2, TF-Me (quant.) Me Me Me Me 44% Williams R. M. et al L 2003, 5, 3135 Williams R. M. et al Tetrahedron 2004, 60, 9503
16 Me Williams Synthesis of Spirotryprostatin A Me a-c Me Me d Me Me d 10% 9% Me 31% Me (a) L-Pro-Bn Cl, BP, Et 3, MeC;(b) 2, Pd/C, Et-Me; (c) WSC, Et3, MeC; (d) p-ts, 2, 3 Å sieves, toluene, 110 C. Abbreviations: BP=benzotriazol-1-yloxy-tris(dimethylamino)phosphonium hexafluorophosphate; WSC= 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride 44% Me 9-epi-Spirotryprostatin A Me 2% Spirotryprostatin A 43% Me Spirotryprostatin A
17 Me orne s Synthesis of Spirotryprostatin B ---Spirocylization Induced by Acyliminium C 2 C 3 C 2 C 3 C 2 C 3 2 CS Ac/C2 23 C, 20min 70% 2 Cl C C 2 Cl 2 MgS 4 95% Cl 1. -Troc-Pro-Cl 2. TFA C18 epimer of 10 2% and C18 epimer of 11 7% 18 Zn Me reflux C 2 C 3 Troc 11 19% 10 37% orne D. A. et al ACIEE 2004, 43, 5357
18 Me orne s Synthesis of Spirotryprostatin B a 10 20% 15% Spirotryprostatin B 20% a) LiMDS(3 equiv),tf, 0 C, 30 min; then SeCl (3 equiv), 3 h, 0 C; then SeCl (3 equiv), 23 C, 16 h.
19 Me orne s Synthesis of Spirotryprostatin A C 2 C 3 C 2 C 3 C 2 C 3 2 BS Ac/C 2 23 C, 20 min 56% Br 2 Br C Br Br 1. -Troc-Pro-Cl 2. TFA Br 9 30% Br 8 26% Zn Me reflux Br C 2 C 3 Troc orne D. A. et al L 2004, 6, 4249
20 Me orne s Synthesis of Spirotryprostatin A CuI ame DMF Br 8 Me Spirotryprostatin A 11% Me 17%
21 Me verman s Synthesis of Spirotryprostatin B η 3 allylpalladium Capture Asymmetric eck Cylization Spirotryprostatin B 2 IL 2 Pd verman L. E. et al ACIEE 2000, 39, 4596
22 Me verman s Synthesis of Spirotryprostatin B Me 2 C Spirotryprostatin B SEM ,18-bis-epi-Spirotryprostatin B 1. Ac 2, pyridine 2. MgBr 2 Et 2 ; ipr 2 Et, Ac (94%, >20:1 E:Z) Me 2 AlCl; ipr 2 Et (93%) Me 2 AlCl; ipr 2 Et (93%) SEM Me 2 C SEM Ac Li 2. TBDPS-Cl 3. 2-iodoaniline, 1-methyl-2-chloropyridinium iodide (78%) [Pd 2 (dba) 3 ] CCl 3 (otol) 3 P, KAc TF, 70 C (72%, 19:20 = 1:1) I 1. SEM-Cl, a 2. TBAF I TBDPS 3. Dess Martin oxid. tbuk (61%) SEM P(Me) 2
23 Me Fuji s Synthesis of Spirotryprostatin B 2 2 nbuli, Et 2 Cl, Me TBDMS Me TBDMS 2 86%, 97% ee 93% Fuji K. et al Synlett 1995, 367
24 Me Fuji s Synthesis of Spirotryprostatin B 2 a C b 55% 91%(1:1) C Bn c 48%(1:1) Me Boc e C 2 Me CbzBn d C CbzBn 69% 87% a) TiCl 3 (20% aqueous, 5.0 equiv), 4 Ac (5.0 equiv),me: 2 (4:1), rt, 3 h; b) i. Bn 2 (1.0 equiv), DCM, rt, 3 h;ii. TMSC (1.05 equiv), rt, 3 h; c) CbzCl (1.2 equiv), Et 3 (2.4 equiv), DCM, rt, 12 h; (d) i. K 2 C 3, Me, rt, 6 h; ii. aqueous 1M Cl, rt, 0.5 h; (e) i. Pd black (80 wt %), 5% C 2 in Me,20 min; ii. -Boc-L-prolide (1.1 equiv), WSC (1.2 equiv), DMC,12 h Fuji K. et al L 2002, 4, 249
25 Me Fuji s Synthesis of Spirotryprostatin B Me Boc a 85% Me Boc b C 2 C 3 Boc 23% c C 2 C 3 Boc spirotryprostatin B 21% 9% 23% 10% 24% a) i. m-cpba (1.1 equiv), DCM, 0 C, 6 h; ii. SeSe (0.6 equiv), ab 4 (1.2 equiv), Me, reflux, 10 h; iii. 30% 2 2 (20 equiv), TF, 0 C, 6 h. b) p-tsa (10 mol %), C 3 C, reflux, 25 min; c) i. LiMDS, TF, 0 C, 30 min; ii. SeCl, TF, 0 C, 2h; iii. DMD, TF, 0 C, 4 h; iv. 4 M Cl in dioxan, 0 C, 30 min; v. Et 3, DCM, 4 h.
26 Me Carreira s Synthesis of Spirotryprostatin B 2 a 71% Me Me b Me I MgI Me Me TIPS TIPS 93% c TIPS 68% dr = 6:1 Me Me or TIPS MgI I TIPS a) Piperylene, [{Rh(Ac)2}2] (1 mol%), benzene, reflux, slow addition of 8 in C 2 Cl 2 ; b) MgI 2 (1 equiv), TF, sealed tube, 75 C;c) [Pd(P 3 ) 4 ] (6 mol%), DMBA, C 2 Cl 2, 30 C. TIPS=triisopropylsilyl,DMBA=1,3-dimethylbarbituric acid. Carreira E. M. et al ACIEE 2003, 42, 694 Carreira E. M. et al JACS 2005, 127, 11505
27 Me Carreira s Synthesis of Spirotryprostatin B Me Me a b,c Boc 45% 97% Boc TIPS TIPS TIPS d,e 89% C 2 Me Boc g C 2 Me Boc f 99% C 2 Me Boc a) Et 3, Boc-l-ProCl, C 2 Cl 2, RT; b) M 2, s 4 (4 mol%), TF/tBu/ 2 4:4:1, RT; c) Pb(Ac) 4, EtAc, rt; d) acl 2, 2-methyl-2-butene, tbu, p 3.6 buffer, rt; e) C 2 2, Et 2, RT; f) TBAF, TF, rt; g) 2, Pd/BaS 4 (33 wt%), quinoline, Et, RT; TIPS
28 Me Carreira s Synthesis of Spirotryprostatin B C 2 Me Boc a,b 77% C 2 Me Boc c S C 2 Me Boc 78% d 74% C 2 Me Boc c 74% Spirotryprostatin B a) M 2,s 4 (1 equiv), TF/tBu/ 2 4:4:1, rt; b) Pb(Ac) 4, EtAc, rt; c) LMDS, TF, 78 C; d) 1. SeCl, LMDS, TF,0 C; 2. DMD, TF, 0 C; e) i. TFA, C 2 Cl 2, RT; ii. Et 3, C 2 Cl 2, rt.
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