Cataly&c Asymmetric Synthesis of All Carbon Oxindole Quaternary Centers. Yong Guan March 18, 2009
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1 Cataly&c Asymmetric Synthesis of All Carbon xindole Quaternary Centers Yong Guan March 18, 2009
2 Importance of xindoles HC 2 H (-)-physostigmine Isolated from the seeds of the African Calabar bean in 1864 Therapeutic agent for treating Alzheimer' disease Jobst, J., et al. Ann. Chem. arm. 1864, 129, 115. Takano, S., et al. Alkaloids 1989, 36, 225. Br H flustramine B Isolated from a marine bryozoan Hino, T, et al. Alkaloids 1989, 34, 1. H H diazonamide A Anti-cancer H H Cl Cl H Lindquist,, et al. J. Am. Chem. Soc. 1991, 113, 2303
3 etrosynthe&c Pathways towards xindoles 1 C 2 4 X 3 b a 1 1 b c a 1 b 2 c b a X C TBS
4 Asymmetric Heck eac&on 1 C 2 4 X 3 b a 1 1 b c a 1 b 2 c b a X C TBS
5 Different Pathways for Asymmetric Heck eac&on Cationic pathway 5 mol% Pd 2 (dba) 3 10 mol% ()-BIAP Ag 3 P 4 (2 equiv.), C 2, 80 C, 26 h S 81%, 71% ee I 10 mol% Pd 2 (dba) 3, 23 mol% ()-BIAP 1,2,2,6,6-pentamethylpiperidine (5 equiv.), DMA, 80 C, 140 h eutral pathway 77%, 66% ee Ashimori, A.; verman, L. E. J. rg. Chem. 1992, 57, 4571.
6 Substrate Scope for Spirocyclic Products I 5 mol% Pd 2 (dba) 3 10 mol% ()-BIAP Ag 3 P 4 (2 equiv.), DMA or PMP (5 equiv.), DMA Ag 81%, 71% ee PMP 77%, 66% ee SEM Bn C 2 Ag 76%, 65% ee PMP 74%, 75% ee Ag 91%, 41-50% ee PMP 66%, 66% ee Ag 90%, 64% ee PMP 68%, 8% ee Ag 99%, 72% ee PMP 89%, 71% ee Ag 88%, 63% ee PMP 91%, 25% ee HC Ag 80%, 45% ee PMP 41%, 72% ee Ashimori, A.; Bachand, B.; verman, L. E.; Poon, D. J. J. Am. Chem.Soc. 1998, 120, 6477.
7 α,β Unsaturated Anilide Substrates TIPS I (Z)-4-siloxy-2-methyl-2-butenanilide 5 mol% Pd 2 (dba) 3 12 mol% ()-BIAP Ag 3 P 4 (2 equiv.), DMA or PMP (4 equiv.), DMA 100 C TIPS Ag E/Z=4:1, 73%, 80% ee PMP E/Z=32:1, 87%, 90% ee TIPS I (E)-4-siloxy-2-methyl-2-butenanilide 5 mol% Pd 2 (dba) 3 12 mol% ()-BIAP Ag 3 P 4 (2 equiv.), DMA or PMP (4 equiv.), DMA 100 C TIPS Ag E/Z=1:0, 80%, 38% ee PMP E/Z=3:1, 85%, 45% ee Ashimori, A.; Bachand, B.; verman, L. E.; Poon, D. J. J. Am. Chem.Soc. 1998, 120, 6488.
8 (Z) α,β Unsaturated Anilide Substrates TIPS 5 mol% Pd 2 (dba) 3 12 mol% ()-BIAP PMP (4 equiv.), DMA TIPS I 100 C E/Z=32:1, 87%, 90% ee TBDMS E/Z=24:1, 80%, 92% ee E/Z=9:1, 76%, 89% ee 89%, 85% ee TIPS tbu TIPS TIPS E/Z=9:1, nd, 19% ee E/Z=19:1, 76%, 0% ee E/Z=49:1, 93%, 91% ee Ashimori, A.; Bachand, B.; verman, L. E.; Poon, D. J. J. Am. Chem.Soc. 1998, 120, 6488.
9 Bidentate vs Monodentate osphine Ligands TBDMS 5 mol% Pd 2 (dba) 3 12 mol% ligand TBDMS I PMP (4 equiv.), DMA 100 C P 2 P 2 P 2 P 2 P 2 TBDMS ipr CH 2 E/Z=24:1, 92% ee E/Z=1.2:1, 23% ee E/Z=1.4:1, 27% ee E/Z=1.3:1, 19% ee Both phosphanes of BIAP are coordinated to Pd in the enantioselective step Ashimori, A.; Bachand, B.; verman, L. E.; Poon, D. J. J. Am. Chem.Soc. 1998, 120, 6488.
10 Chiral Amplifica&on Studies The catalyst is monomeric Pd-BIAP Ashimori, A.; Bachand, B.; verman, L. E.; Poon, D. J. J. Am. Chem.Soc. 1998, 120, 6488.
11 Cataly&c Cycle for Ca&onic Pathway TIPS I * P Pd P I AgY AgI Y = 1/3 P 4 3- * P P Pd TIPS * P Pd P TIPS Y - HY 2 Y * P Pd P TIPS H Y H TIPS * P Pd P Y 5-exo-trig Ashimori, A.; Bachand, B.; verman, L. E.; Poon, D. J. J. Am. Chem.Soc. 1998, 120, 6488.
12 chanism for eutral Pathway ArX + P * Pd P * P Pd P Ar X Cationic and neutral pathways give opposite enantiomers with different ee s X L L L H Pd Cl H Pd Cl 1.4 ev 0.3 ev Insertions from five coordinate intermediates have much higher barriers than those from four coordinate intermediates L L L H Pd Cl H Pd Cl P Ar P * Pd * Pd P P * X - P Pd Ar P X + Ar X Ashimori, A.; Bachand, B.; verman, L. E.; Poon, D. J. J. Am. Chem.Soc. 1998, 120, Thorn, D. L.; Hoffmann,. J. Am. Chem. Soc. 1978, 100, 2079.
13 Transi&on State Models Pd β P P * closest C-C contact β-methyl to pseudoequatorial phenyl on P Favored 3.2 Å 3.2 Å Disfavored 2.9 Å 2.8 Å aryl-phenyl interaction P P P P Favored Disfavored Alkene π and aryl C-Pd σ bonds are nearly coplanar Ashimori, A.; Bachand, B.; verman, L. E.; Poon, D. J. J. Am. Chem.Soc. 1998, 120, 6488.
14 Applica&on in Total Synthesis PF 6 - H 1) ed-al; I 2 2) TIPSTf 3) tbuli, Et 2, -78 C, C 2 H 2 C TIPS 1) P( 2) 3 Et 3 2) I I TIPS 70% H 67% TIPS 10 mol% Pd 2 (dba) 3 23 mol% (S)-BIAP 3 HCl, 23 C 1,2,2,6,6-pentamethylpiperidine, DMA, 100 C E/Z=98:2, 95% ee 84% (2 steps), 95% ee 99% ee CH recryst. (80%) H 3 Cl, Et 3, MgS 4 LiAlH 4, THF, reflux H BBr 3 ; a; C HC 2 H 88%, (-)-esermethole 63%, (-)-physostigmine Ashimori, A.; Matsuura, T.; verman, L. E.; Poon, D. J. J. rg. Chem. 1993, 58, 6949.
15 Asymmetric Amide α Aryla&on 1 C 2 4 X 3 b a 1 1 b c a 1 b 2 c b a X C TBS
16 Asymmetric Amide α Aryla&on Br Bn 5 mol% 5 mol% Pd(dba) 2 BF 4 - atbu (1.5 equiv.), DME, rt, 24 h Bn 75%, 76% ee i-bu 27%, 70% ee 74%, 57% ee 95%, 42% ee 87%, 50% ee Lee, S.; Hartwig, J. F. J. rg. Chem. 2001, 66, 3402.
17 Cataly&c Cycle for Amide α Aryla&on Br PdL 2 L L L Pd L Br Pd abr + HtBu atbu Lee, S.; Hartwig, J. F. J. rg. Chem. 2001, 66, 3402.
18 Modifica&ons Br 5 mol% Pd 2 (dba) 3 10 mol% Ligand atbu, DME, rt, 14 h tbu - Tf tbu 95%, 43% ee Br 10 mol% Pd(Ac) 2 20 mol% Ligand LitBu (2 eq.), DME 100 C, 12 h BF 4-62%, 61% ee F 59%, 65% ee 51%, 54% ee Glorius, F.; Altenhoff, G.; Goddard,.; Lehmann, C. Chem. Commun. 2002, Arao, T.; Kondo, K.; Aoyama, T. Tetrahedron Lett. 2006, 47, 1417.
19 Kündig s Improvement tbu tbu Br 5 mol% 5 mol% Pd(Ac) 2 atbu, DME rt, 24 h I - 99%, 94% ee 99%, 93% ee 99%, 93% ee 98%, 86% ee 98%, 93% ee Bn 72%, 79% ee 96%, 95% ee 94%, 84% ee Kündig, E. P.; Seidel, T. M.; Jia, Y.-X.; Bernardinelli, G. Angew. Chem., Int. Ed. 2007, 46, 8484.
20 Asymmetric Cycliza&on of Silyloxy 1,6 Enynes 1 C 2 4 X 3 b a 1 1 b c a 1 b 2 c b a X C TBS
21 Asymmetric Cycliza&on of Silyloxy 1,6 Enynes P P TBS 10 mol% (()-Binaphane)Pd(H) 2 (Tf) : 1 Et 2 /AcH, rt TBS 1 [Pd] exo-dig Ac Bz Ac (20 min, 83%, 91% ee) (20 min, 67%, 82% ee) Corkey, B. K.; Toste, F. D. J. Am. Chem. Soc. 2007, 129, 2764.
22 Asymmetric Cyanoamida&on 1 C 2 4 X 3 b a 1 1 b c a 1 b 2 c b a X C TBS
23 Asymmetric Cyanoamida&on P Bn C (8 mol%) Pd(dba) 2 (2 mol%) DMPU (1 equiv.) decalin, 100 C, 24 h Bn C quant., 81% ee TBS Bn C quant., 72% ee Bn 72%, 68% ee C Bn 94%, 74% ee C Cl Bn C quant., 82% ee Yasui, Y.; Kamisaki, H.; Takemoto, Y. rg. Lett. 2008, 10, 3303.
24 Cataly&c Cycle for Cyanoamida&on ' C PdL n ' C ' C Pd L n ' C Pd L amidopalladation Yasui, Y.; Kamisaki, H.; Takemoto, Y. rg. Lett. 2008, 10, 3303.
25 Asymmetric Alkyla&ons 1 C 2 4 X 3 b a 1 1 b c a 1 b 2 c b a X C TBS
26 Asymmetric Allylic Alkyla&on (AAA) X Br Y Pd(Ac) 2 PCy 3 atbu Y Y X Br X AAA X Cl Y Pd(Ac) 2 PCy 3 atbu Trost, B. M.; Frederiksen, M. U. Angew. Chem., Int. Ed. 2005, 44, 308.
27 Cataly&c Cycle for AAA 1 ' 1 ' 2 Decomplexation 2 L L M M=Pd, Mo ' Ac 1 ' L M L 1 L M L ' Complexation 2 ucleophilic addition 1 2 L M L ' L M L Ac ' Ionization 2 L M L ' Trost, B. M.; Crawley, M. L. Chem. ev. 2003, 103, 2921.
28 Linear or Branched Products in AAA Mo cat. 2 H Ac Pd cat. 2 Pd 4d 10 coordination number 2 to 4 direct attack of the nucleophiles on the π-allyl from the face opposite Pd Mo 4d 5 5s 1 coordination number 4 to 8 nucleophiles precoordinating to Mo Belda,.; Moberg, C. Acc. Chem. es. 2004, 37, 159.
29 Pd Catalyzed AAA P 2 2 P H H 5 mol% Cl Pd Pd Cl (, )-L anthracenyl Ac (2.5 mol%) (1.1 equiv.) 93%, 81% ee, tbuh (4 equiv.) -78 to 4 o C, 12 h 75%, 80% ee 96%, 77% ee 75%, 70% ee Trost, B. M.; Frederiksen, M. U. Angew. Chem., Int. Ed. 2005, 44, 308.
30 Substrate Scope for Pd Catalyzed AAA P 2 2 P H H 5 mol% Cl Pd Pd Cl (, )-L anthracenyl Ac (2.5 mol%) (1.1 equiv.) 93%, 81% ee, tbuh (4 equiv.) -78 to 4 o C, 12 h F 72%, 97% ee 73%, 75% ee 83%, 74% ee Trost, B. M.; Frederiksen, M. U. Angew. Chem., Int. Ed. 2005, 44, 308.
31 Protec&ng Groups in Pd Catalyzed AAA P 2 2 P H H 5 mol% Cl Pd Pd Cl (, )-L anthracenyl Ac (2.5 mol%) (1.1 equiv.) 93%, 81% ee, tbuh (4 equiv.) -78 to 4 o C, 12 h TMS Bn TMS 75%, 70% ee 76%, 80% ee 81%, 68% ee 96%, 66% ee Trost, B. M.; Frederiksen, M. U. Angew. Chem., Int. Ed. 2005, 44, 308.
32 Mo Catalyzed AAA H H + C 2 tbu (1.2 equiv.) (, ) (15 mol%) Mo(C 7 H 8 )(C) 3 (10 mol%) LitBu (2 equiv.), rt 99%, 81% ee HBoc 96%, 91% ee 96%, 95% ee 95%, 80% ee Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2006, 128, 4590.
33 Substate Scope for Mo Catalyzed AAA H H + C 2 tbu (1.2 equiv.) (, ) (15 mol%) Mo(C 7 H 8 )(C) 3 (10 mol%) LitBu (2 equiv.), rt 99%, 81% ee TMS TBS 95%, 80% ee 96%, 88% ee 94%, 75% ee Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2006, 128, 4590.
34 Protec&ng Groups in Mo Catalyzed AAA Bn H H Bn + C 2 tbu (1.2 equiv.) (, ) (15 mol%) Mo(C 7 H 8 )(C) 3 (10 mol%) LitBu (2 equiv.), rt 95%, 93% ee Bn Bn Bn MM 95%, 87% ee Bn 92%, 87% ee allyl 99%, 88% ee Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2006, 128, 4590.
35 Models for Enan&odiscrimina&on in Mo Catalyzed AAA C Mo C Mo 1 C 2 2 C 1 Favored Disfavored 1 1 S 2 2 Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2006, 128, 4590.
36 Applica&on in Total Synthesis + C 2 tbu (1.2 equiv.) H H (, ) (15 mol%) Mo(C 7 H 8 )(C) 3 (10 mol%) LitBu (2 equiv.), rt 98%, 82% ee s 4, M ai 4 92%, 82% ee 66%, 99% ee CH 72% H 2, Et 3 LAH, THF, reflux H (-)-esermethole after 2 recrystalization BBr 3 ; a; HC 2 C H (-)-physostigmine Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2006, 128, 4590.
37 Mo Catalyzed AAA Ar + C 2 tbu H H (, ) (15 mol%) Mo(C 7 H 8 )(C) 3 (10 mol%) atbu (1.1 equiv.), 60 C, THF Ar + Ar (1.1 equiv.) branched product Linear product Boc MM Bn b/l=5:1, dr=5:1 91%, 93% ee b/l=19:1, dr=7:1 90%, 92% ee b/l=17:1, dr=9:1 85%, 90% ee b/l=18:1, dr=8:1 88%, 92% ee Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2007, 129,
38 Substrate Scope for Mo Catalyzed AAA Ar + C 2 tbu H H (, ) (15 mol%) Mo(C 7 H 8 )(C) 3 (10 mol%) atbu (1.1 equiv.), 60 C, THF Ar + Ar (1.1 equiv.) branched product Linear product C b/l=7:1, dr=4.5:1 84%, 89% ee b/l=18:1, dr=8:1 92%, 92% ee b/l=15:1, dr=19:1 88%, 95% ee b/l=15:1, dr=6:1 90%, 90% ee Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2007, 129,
39 Linear or Branched Products Ar + C 2 tbu H H (, ) (15 mol%) Mo(C 7 H 8 )(C) 3 (10 mol%) atbu (1.1 equiv.), 60 C, THF Ar + Ar (1.1 equiv.) branched product Linear product S S 90% 82% b/l=11:1, dr=19:1 95%, 92% ee Boc b/l=9:1, dr=19:1 65%, 94% ee Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2007, 129,
40 Mo Enolate Structures L Ar L Mo C C Ar -bound enolate Branched product Ar L L Mo C C Ar C-bound enolate Linear product 1) A large aryl group should favor the -bound enolate. (Ar=1-naphth, b/l=15:1) 2) A heterocycle group should favor the C-bound enolate. (Ar=2-thienyl, b/l=0:1) 3) EWG should stablize both enolates and slow down their interconversion. (Ar=4-C-, b/l=7:1) Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2007, 129,
41 Transi&on State Models Ar H Mo(L) favored path A Ar H Ar H Mo(L) disfavored path B H Ar Trost, B. M.; Zhang, Y. J. Am. Chem. Soc. 2007, 129,
42 ase Transfer Catalyzed Asymmetric Alkynyla&on tbu 2 C EWG tbu 2 C + EWG C 2 tbu Cl TIPS 3 mol% H tbu 2 C C 2 Allyl Br + Allyl 33% KF (aq) o-xylene/chcl 3 (7:1) -20 C (1.3 equiv.) 95%, 85% ee Poulsen, T. B.; Bernardi, L.; Alemán, J.; vergaard, J.; Jørgensen, K. A. J. Am. Chem. Soc. 2007, 129, 441.
43 Cataly&c Cycle for ase Transfer Catalysis TIPS C 2 tbu KF K C 2 tbu 4 + H Cl K + Allyl 2 C C 2 tbu 4 C 2 tbu Br C 2 Allyl + KBr K C 2 tbu 4 Allyl C 2 tbu Br Poulsen, T. B.; Bernardi, L.; Alemán, J.; vergaard, J.; Jørgensen, K. A. J. Am. Chem. Soc. 2007, 129, 441.
44 Black type C acyla&on 1 C 2 4 X 3 b a 1 1 b c a 1 b 2 c b a X C TBS
45 Black type C acyla&on of Benzofurans DMAP CH 2 Cl 2 rt ' 2 ' C 2 ' 2 Black, T. H.; Arrivo, S. M.;Schumm, J. S.; Knobeloch, J. M. J. Chem. Soc. Chem. Commun. 1986, Black, T. H.; Arrivo, S. M.;Schumm, J. S.; Knobeloch, J. M. J. rg. Chem. 1987, 52, 5425.
46 Switching from Benzofurans to xindoles C top C C bottom left right Hills, I. D.; Fu, G. C. Angew. Chem., Int. Ed. 2003, 42, 3921.
47 Fu s System: p&miza&on 5 mol% CH 2 Cl 2, 35 C Fe 58% ee Et tbu CCl 3 63% ee ot bserved 99% ee Hills, I. D.; Fu, G. C. Angew. Chem., Int. Ed. 2003, 42, 3921.
48 Substrate Scope in Fu s System CCl 3 5 mol% CH 2 Cl 2, 35 C Fe CCl 3 91%, 99% ee S CCl 3 Bn CCl 3 CCl 3 81%, 95% ee 82%, 94% ee 72%, 93% ee I CCl 3 Bn CCl 3 94%, 98% ee 88%, 98% ee Hills, I. D.; Fu, G. C. Angew. Chem., Int. Ed. 2003, 42, 3921.
49 Transi&on State Model for Fu s System 1 2 Cl 3 C Fe 1) The ee of the product does not erode with time, indicating that C- acylation of the enolate is irreversible 2) 1 H M studies show that the resting state of the catalyst is the catalyst itself (not acylated) Hills, I. D.; Fu, G. C. Angew. Chem., Int. Ed. 2003, 42, 3921.
50 Vedejs System: A ew Catalyst 2 Br 2, K 2 C 3 2 Br tbuli 3 CCH Ac 2 2 H C 3 Ac 58% 2 H C 3 Ac Camphorsulfonic acid esolution, >99% ee 2 H C 3 Ac H 3 S S, 98.3% ee TADMAP: 2,2,3-triphenyl-1-acetoxyethyl DMAP Shaw, S. A.; Aleman, P.; Vedejs, E. J. Am. Chem. Soc. 2003, 125,
51 p&miza&on in Vedejs System 2 H C 3 Ac C 2 10 mol% C 2 rt C 2 C 2 CH 2 Cl 2, 35 d, 23% ee C 2 CH 2 Cl 2, 24 h, 23% ee C 2 CH 2 CCl 3 CH 2 Cl 2, 24 h, 39% ee 2 C 2 CCl 3 CH 2 Cl 2, 24 h, 75% ee tert-amyl alcohol, 0 o C, 24 h, 98%, 78% ee Shaw, S. A.; Aleman, P.; Christy, J.; Kampf, J. W.; Va, P.; Vedejs, E. J. Am. Chem. Soc. 2006, 128, 925.
52 Theore&cal Study for Vedejs System 2 θ 2 Energy minimus DFT computations (B3LYP/6-31G*) Shaw, S. A.; Aleman, P.; Christy, J.; Kampf, J. W.; Va, P.; Vedejs, E. J. Am. Chem. Soc. 2006, 128, 925.
53 Transi&on State Models in Vedejs System c b a H c b a H Favored Disfavored Shaw, S. A.; Aleman, P.; Christy, J.; Kampf, J. W.; Va, P.; Vedejs, E. J. Am. Chem. Soc. 2006, 128, 925.
54 Transi&on State Models in Vedejs System H H 1 C 3 Ac 1 C 3 Ac Favored Disfavored 1 1 Shaw, S. A.; Aleman, P.; Christy, J.; Kampf, J. W.; Va, P.; Vedejs, E. J. Am. Chem. Soc. 2006, 128, 925.
55 AcLeDMAP: An Improved Catalyst tbu HBz H S 3 pyr tbu HBz H 3-Li-DMAP tbu H HBz 2 Ac 2 Et 3 tbu Ac HBz 2 (S)--Benzoyl-tert-leucinol 70% 70%, dr > 98:2 86%, dr > 98:2 AcLeDMAP tbu H Duffy, T. A.; Shaw, A. S.; Vedejs, E. J. Am. Chem. Soc. 2009, 131, 14.
56 Indolyl Acetate Substrate Scope Ac 2 tbu AcCl Et 3 Et 2 Ac DPA 10 mol% 0 C EtAc HBn Ac DPA DPA = C()CH 2 2 h, 94%, 92% ee Ac Bn Ac TBDPS Ac Ac DPA DPA DPA DPA 2.5 h, 98%, 91% ee 3 h, 96%, 94% ee 3 h, 94%, 91% ee 2.5 h, 98%, 86% ee ipr Ac DPA Ac DPA Br Ac DPA 42 h, 82%, 94% ee 2 h, 98%, 66% ee 0.33 h, 95%, 85% ee Duffy, T. A.; Shaw, A. S.; Vedejs, E. J. Am. Chem. Soc. 2009, 131, 14.
57 Conclusions 1 C 2 4 earrangement Heck X Alkylation 1 2 Arylation X Cyanoamidation Cyclization C TBS
58 Acknowledgement Dr. Wulff Dr. Babak, Dr. Smith Li, Hong, Aman, Zhensheng, Anil, Munmun, ilanjana, Dima, Wynter, Alex, Victor All of you
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