Catalytic Reductive Coupling Reactions. Erin Vogel Michigan State University 3:00 p.m. 28 September 2005
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1 Catalytic eductive Coupling eactions rin Vogel Michigan State University 3:00 p.m. 28 September 2005
2 eductive ydrogenation 3P h P3 P3 Wilkinson s Complex 3P P3 h P3 2 P3 P3 h P3 P3 3P h P3 fast P3 h 3P h P3 P3 Jardine, F. Prog. Inorg. Chem. 1981, 28,
3 eductive ydrogenation 3P h P3 P3 Wilkinson s Complex 3P P3 h P3 2 P3 P3 h P3 P3 3P h P3 fast P3 ' h P3 h P3? 3P ' Jardine, F. Prog. Inorg. Chem. 1981, 28,
4 utline iscovery and evelopments of eductive Coupling eactions Pd-catalyzed eactions Ni-catalyzed eactions h-catalyzed eactions 2 as Terminal eductant chanistic Considerations Conclusions
5 utline iscovery and evelopments of eductive Coupling eactions Pd-catalyzed eactions Ni-catalyzed eactions h-catalyzed eactions 2 as Terminal eductant chanistic Considerations Conclusions
6 Cyclopentane Natural Products C2 C511 Prostaglandins Capnellane 2C irsutic Acid C2 Pentalenolactone Trost, B. Chem. Soc. ev. 1982, 11, Cedrene Isocomene Coriolin C2 etigeranic Acid
7 Alder-ne eaction Y Y Y:, N, 3C N Y Y S, 140 oc xylene, 4 d,, etc. 3C N Choong, N.; Sammes, P.; Smith, G.; Ward,. Chem. Comm. 2001,
8 Pd(0)-Catalyzed Allylic Alkylations (3P)4Pd (3-5 mol%) Na, TF, reflux 85% Ac Nu Ac Pd(P3)4 Trost-Tsuji eaction L Pd L Nu L Pd L Ac Nu L Trost, B. Acc. Chem. es. 1980, 13, Pd L Ac
9 Pd(0)-Catalyzed Couplings allyl acetate entry (3P)4Pd (3-5 mol%) Na, TF, reflux allyl acetate enyne enyne yield 1 85% Ac Ac 2 87% 3 Ac Ac 4 Trost, B.; Lautens, M. J. Am. Chem. Soc. 1985, 107, % 71%
10 Alder-ne Cyclization (3P)4Pd 85% FVT 550oC 80% Ac (3P)4Pd 87% FVT 78% Trost, B.; Lautens, M. J. Am. Chem. Soc. 1985, 107, Trost, B.; Lautens, M.; Chan, C.; Jebartham, ; Mueller, T. J. Am. Chem. Soc. 1991, 113,
11 iscovery of eductive Cyclization Ac (3P)4Pd 24 hr, 65 oc 35% Ac (3P)4Pd 24 hr, 65 oc 85% 650 oc No eaction Ac (3P)4Pd 24 hr, 65 oc 85% 675 oc ecomposition Trost, B. Acc. Chem. es. 1980, 13, Trost, B.; Lautens, M. J. Am. Chem. Soc. 1985, 107, Trost, B.; Lautens, M.; Chan, C.; Jebartham, ; Mueller, T. J. Am. Chem. Soc. 1991, 113,
12 iscovery of eductive Cyclization ypothesis: Pd(0) 2 Pd(2+) Pd (2+) solvent, rt Ac Pd(0) 65 oc Pd(2+) rt Trost, B.; Lautens, M. J. Am. Chem. Soc. 1985, 107, Trost, B.; Lautens, M.; Chan, C.; Jebartham, ; Mueller, T. J. Am. Chem. Soc. 1991,113,
13 Screening Pd(2+) Catalysts catalyst solvent entry catalyst solvent temperature time (h) yield (%) 1 (3P)4Pd TF reflux Pd(Ac)2 TF room temp. not reported 50 3 (3P)2Pd(Ac)2 TF 64 C (3P)2Pd(Ac)2 C C Trost, B.; Lautens, M. J. Am. Chem. Soc. 1985, 107,
14 Catalytic eductive Cyclization enyne entry allyl acetate (3P)2Pd(Ac)2 (5 mol%) 3P (5 mol%), C66, product enyne product yield 1 85% Ac 2 87% 4 68% Ac Ac 85% Ac 3 yield 87% Trost, B.; Lautens, M. J. Am. Chem. Soc. 1985, 107, % 71% 64%
15 Catalytic eductive Cyclization enyne entry allyl acetate (3P)2Pd(Ac)2 (5 mol%) 3P (5 mol%), C66, product enyne product yield 1 85% Ac 2 87% 4 68% Ac Ac 85% Ac 3 yield 87% Trost, B.; Lautens, M. J. Am. Chem. Soc. 1985, 107, % 71% 64%
16 1,3-iene vs. 1,4-iene Formation ' ' Pd(+4) L2Pd2 α β a ' ' β elimination Pd(+4) L b a ' Pd(+4) a Pd(+4) a path a ' and/or = L ' a b ' ' b ' path b ' or = Pd(+4) b b a Trost, B.; Lautens, M. J. Am. Chem. Soc. 1985, 107, ' a '
17 Pd-Catalyzed Cycloisomerizations a n n b ' b a (+4) ' (+2) Pd n ' (+4) Pd n or a Pd (+2) n b b ' a Pd n ' ' (+4) n Pd a b ' Trost, B.; Lautens, M.; Chan,.; Jebaratnam,.; Muller, T. J. Am. Chem. Soc. 1994, 116,
18 utline iscovery and evelopments of eductive Coupling eactions Pd-catalyzed eactions Ni-catalyzed eactions h-catalyzed eactions 2 as Terminal eductant chanistic Considerations Conclusions
19 Nickel Catalyzed Coupling eactions Bu 1 1 Ni(C)2 5 mol% L L Ni 1 Bu2Zn/ BuZn a P3 25 mol % 1 b entry ligand 1 yield (%a) yield (%b) P P P3 Bu Montgomery, J.; Savchenko, A. J. Am. Chem. Soc. 1996, 118,
20 Proposed Coupling chanism 2 Ni L 2 1 Ni(C)2 1 L L L Ni ZnBu2 (transmetallation) BuZn LnNi 2 1 reductive elimination L = TF or 1 β-hydride elimination L = P3 with P3 without P3 1 BuZn 2 LnNi 2 1 reductive coupling Montgomery, J.; blinger,.; Savchenko, A. J. Am. Chem. Soc. 1997, 119, Montgomery, J. Acc. Chem. es. 2000, 33, Bu 2 alkylative coupling
21 Stereoselective Preparation of Allylic Alcohols t Znt2 Ni(C)2 67% Znt2 Ni(C)2 : PBu3 1:4 62% ZnBu2 Ni(C)2 Bu 71% ZnBu2 Ni(C)2 PBu3 blinger,.; Montgomery, J. J. Am. Chem. Soc. 1997, 119, Bu
22 eductive Coupling of Alkynes and Aldehydes ZnBu2 Ni(C)2 PBu3 n-ept 100 mol% entry 100 mol% Ni(C)2 (10 mol%) phosphine (20 mol%) t3b (200 mol%) TF, 23 oc, 18 h phosphine yield (%) regioselectivity 1 Cy3P : 23 2 t3p : 9 3 (n-bu)3p : 8 blinger,.; Montgomery, J. J. Am. Chem. Soc. 1997, 119, uang, W.; Chan, J.; Jamison, T. rg. Lett. 2000, 26, Bu Ni(C)2 (10 mol%) (n-bu)3p (20 mol%) t3b (200 mol%) toluene, 0 oc, 18 h n-ept 45%
23 eductive Couplings of Allenes and Aldehydes 1 2 entry 1 2 Si3 3Si Ar product allene n-pr Cy cat. Ni(C)2 NC-iPr (1) TF 1 N Ar i-pr i-pr 2 NC-iPr (1) allylic: yield (allylic) site ee homoallyic selectivity (%) Z/ n-pr N Sit3 n-pr i-pr i-pr 94 : 6 80% >95:5 NA : 7 76% >95:5 >95:5 98 n-pr Sit3 Ng, S-S.; Jamison, T. J. Am. Chem. Soc. 2005, 127,
24 Proposed Coupling Scheme Cy Sit3 t3si cat. Ni(C)2 NC-iPr (1) TF cat. Ni(C)2 NC-iPr (1) TF = Sit3 Cy L Cy Ni Cy Cy Cy Ni L t3si L Ni Cy Cy Ni Ng, S-S.; Jamison, T. J. Am. Chem. Soc. 2005, 127, L
25 Ni-Catalyzed eductive Couplings of poxides Ni(C)2 (10 mol%) Bu3P (20 mol%) t3b (200 mol %) ether, 3h exo endo entry yield (%) regioselectivity (endo:exo) 1 C2 45 >95:5 2 NBn 65 >95:5 3 C(C2)2 88 >95:5 Molinaro, C.; Jamison, T. J. Am. Chem. Soc. 2003, 125,
26 chanism for Ni-Catalyzed eductive Coupling Ni(C)2 (10 mol%) Bu3P (20 mol%) t3b (200 mol%) ether, 3h Bu3P Ni 6-exo-dig cyclization LnNi-PBu3 Bu3P Ni PBu3 Bt2 t Molinaro, C.; Jamison, T. J. Am. Chem. Soc. 2003, 125, Ni PBu3 t3b Bt2 Ni
27 Total Synthesis of Amphidinolide T1 and T4 C2 * alkyne-aldehyde * nickel-catalyzed reductive coupling (intramolecular) nickel-catalyzed alkyne-epoxide reductive coupling (intermolecular) amphidinolide T1 amphidinolide T4 TBS N * C2 Ni(C)2 (10 mol%) Bu3P (20 mol%) t3b, TBS TMS 81% yield >99% dr TMS 40-44% yield >95:5 dr Colby,. Brien, K.; Jamison, T. J. Am. Chem. Soc. 2005, 127,
28 Total Synthesis of Amphidinolide T1 and T4 C2 * alkyne-aldehyde * nickel-catalyzed reductive coupling (intramolecular) * C2 nickel-catalyzed alkyne-epoxide reductive coupling (intermolecular) amphidinolide T4 amphidinolide T1 44%, >10:1 dr 3 1. Ni(cod)2 (20 mol%) PBu3 (40 mol%) t3b, toluene, 60oC 3 70% amphidinolide T1 2. TBS, imid. TBS 3. 3; 2S 31% >10:1 dr Colby,. Brien, K.; Jamison, T. J. Am. Chem. Soc. 2005, 127, amphidinolide T4 74%
29 utline iscovery and evelopments of eductive Coupling eactions Pd-catalyzed eactions Ni-catalyzed eactions h-catalyzed eactions 2 as Terminal eductant chanistic Considerations Conclusions
30 h-catalyzed Intramolecular Alder-ne eactions 1 P 2 2 P dppb = 1,4-Bis(diphenylphosphino)butane Catayst AgSbF6 C2C2 1 * P2 2P (S)-BINAP 2 1 entry 1 2 catalyst ligand product yield (%) ee (%) 1 t [h(c)] a < [h(c)]2 dppb 2b t [h(c)]2 ()-BINAP (-)-2c 96 > Ac [h(c)]2 (S)-BINAP (+)-2d t [h(c)]2 (S)-BINAP (+)-2e 93 > 99 6 Ac [h(c)]2 ()-BINAP (-)-2f 96 >99 Cao, P.; Wang, B.; Zhang,. J. Am. Chem. Soc. 2000, 122, Lei, A.; e, M.; Wu, S.; Zhang,. Angew. Chem. Int. d. 2002, 41,
31 chanism via xidative Cyclometallation [hi]+ M = [hiii]+ [hi]+ M c M b x = alkyl,, Ac, Bz, Tong,.; Li,.; Zhang, Z.; Zhang,. J. Am. Chem. Soc. 2004, 126, a
32 Intramolecular alogen Shift 10 mol% h(p3)3 C/ reflux 92% Yield 10 mol% h(p3)3 C/ reflux 73% Yield Tong,.; Zhang, Z.; Zhang,. J. Am. Chem. Soc. 2003, 125,
33 chanism via xidative Cyclometallation M = Ac, Bz M M = [hiii]+ M =, Br Pd3 Y 2- Pd trans-elimination Y Y- ates of heteroatom (Y) elimination: β halide > β Ac > β > β ~ β Tong,.; Li,.; Zhang, Z.; Zhang,. J. Am. Chem. Soc. 2004, 126, Zhang, Z.; Lu,.; u, Z.; Zhang, Q.; an,. rganometallics 2001, 20, Pd4
34 chanism via xidative Cyclometallation [hi]+ M = [hiii]+ [hi]+ M c M b Tong,.; Li,.; Zhang, Z.; Zhang,. J. Am. Chem. Soc. 2004, 126, Amii,.; Kishikawa, Y.; Uneyama, K. rg. Lett. 2001, 3, a
35 eaction chanism via π-allyl hodium Species hi M M= hi LnhIII M Tong,.; Li,.; Zhang, Z.; Zhang,. J. Am. Chem. Soc. 2004, 126,
36 Total Synthesis of (+)-Blastmycinone C37 C37 C37 (-)-Blastmycinolactol n-bu i-bu2c N C37 C (+)-Antimycin (+)-Blastmycinone C511 (±) C511 [h(c)]2 ()-BINAP AgSbF6 95% C511 47%, >99% ee, M.; Lei, A.; Zhang,. Tetrahedron Lett. 2005, 46, %, >99% ee
37 utline iscovery and evelopments of eductive Coupling eactions Pd-catalyzed eactions Ni-catalyzed eactions h-catalyzed eactions 2 as Terminal eductant chanistic Considerations Conclusions
38 C-C Bond Formation with 2 as Terminal eductant Ac 3P 3P h P3 C -P3 1 mol% [h(c)2acac] C/2 (1:1), 80oC 80% yield 3P Ac 3P h C 3P h P3 C 3P C P3 3P h C Ac 3P syn 22% h ydroformylation 2 anti 78% 3P h P3 C 3P 3P h C C Breit, B. Acc. Chem. es. 2003, 36, vans,.; sborn, J.; Wilkinson, G. J. Chem. Soc. A 1968, C
39 Intramolecular eductive Aldolization Catalyst (10 mol%) Ligand (24 mol%) 2 (1 atm), Addditive (30 mol%) C, 25 oc entry catalyst ligand additive yield aldol (syn:anti) yield 1,4-reduction 1 h(p3) % (99:1) 95% 2 h(c)2tf P % (99:1) 25% 3 h(c)2tf P3 KAc 59% (58:1) 21% 4 h(c)2tf (p-cf3)3p % (14:1) 22% 5 h(c)2tf (p-cf3)3p KAc 89% (10:1) 0.1% Jang,.; uddleston,.; Krische, M. J. Am. Chem. Soc. 2002, 124,
40 eductive ydrogenation h 3P P3 P3 Wilkinson s Complex 3P P3 h P3 2 P3 P3 h P3 PP3 3P P3 ' h P3 3P h P3? h P3 omolytic ydrogen Activation ' Jardine, F. Prog. Inorg. Chem. 1981, 28,
41 eterolytic ydrogen Activation 3P 3P P3 h 2 P3 3P 3P h Lnh 2 B ' B 3P 3P Lnh h P3 2 3P (Base) 3P Lnh B+ - (Base) 3P 3P P3 h ' 3P ' Brothers, P. Prog. Inorg. Chem. 1981, 28, P3 h 3P h P3
42 Addition of Aldehyde nolates to Ketones C3 h(c)2tf (10 mol%) (2-furyl)3P (24 mol%) 2 (1 atm) K2C3 (100 mol%) TF, 40 oc n m 1a, n = 1, m = 1 n C3 m 1b-4b, Yield %, syn:anti, 2a, n = 2, m = 1 (Yield % 1,4 eduction) 3a, n = 1, m = 2 4a, n = 2, m = 2 C3 1b, 72%, 2:1 (16%) C3 2b, 73%, 10:1 (21%) Koech, P.; Krische, M. rg. Lett. 2004, 6, C3 3b, 63%, 5:1 (30%) C3 4b, 59%, 4:1 (29%)
43 Proposed Catalytic chanism Conjugate eduction - (Base) Conjugate eduction Manifold isabled C3 LnhIII C3 LnhI C3 C3 i-ydride Catalytic Cycle LnhI LnhIII(2) - (Base) LnhI Mono-ydride Catalytic Cycle Ln()2hIII 2 3C Koech, P.; Krische, M. rg. Lett. 2004, 6, C3 C3 LnhI C3 2
44 Catalytic Cycloreduction mploying euterium 3C h(c)2tf (10 mol%) 3P (24 mol%) 2 (1 atm) K2C3 (80 mol%) C, 80oC uddleston,.; Krische, M. rg. Lett. 2003, 5, C3 83% isolated yield No 1,4 eduction
45 eductive Condensation Continued 200 mol% 100 mol% Lnh(I) (5 mol%) osphine C (0.1 M), 25 oc 2 (1 atm) 2P 1b-4b P2 BIPP S 2-Nap 1b 86% 2b 89% 3b 78% 4b 70% No Basic Additives Needed--eterolytic ydrogen Activation?? Jang,.; uddleston,.; Krische, M. J. Am. Chem. Soc. 2004, 126,
46 Proposed Catalytic chanism Conjugate eduction - (Base) Conjugate eduction Manifold isabled C3 LnhIII C3 LnhI C3 C3 i-ydride Catalytic Cycle LnhI LnhIII(2) - (Base) LnhI Mono-ydride Catalytic Cycle Ln()2hIII 2 C3 LnhI Koech, P.; Krische, M. rg. Lett. 2004, 6, C3 C3 2
47 eductive Condensation Continued Predicted xperimental h(c)2tf (5 mol%) BIPP (5 mol%) C (0.1 M), 25 oc 2 (1 atm) No Basic Additives Needed--eterolytic ydrogen Activation?? Jang,.; uddleston,.; Krische, M. J. Am. Chem. Soc. 2004, 126,
48 Possible chanisms for eductive Coupling hiln ydrometallative chanism eterolytic 2 Activation LnhI - 2 hiiiln LnhI hiln 2 LnhI LnhI - xidative Coupling chanism eterolytic 2 Activation LnhIII 2 2 hiii()2ln hiii()2ln LnhI LnhIII()2 - hiiiln hiii()ln 2 ydrometallative chanism omolytic 2 Activation LnhI hiii()ln xidative Coupling chanism omolytic 2 Activation LnhIII 2 2 Jang,.; Krische, M. J. Am. Chem. Soc. 2004, 126, hiiiln
49 eductive Cyclization of iynes h(c)2tf (3 mol%) rac-binap or BIPP (3 mol%) C (0.1M), 25 oc 2 (1 atm) 2 3C2C C3 TsN 3C2C 1b, 85% 2b, 78% C3 4b, 62% 3b, 89% h(c)2tf (5 mol%) BIPP (5 mol%) C (0.1 M), 25oC 2 (1 atm) Jang,.; Krische, M. J. Am. Chem. Soc. 2004, 126,
50 ydrometallative Catalytic chanism egio-etermining C- Bond Formation Precedes C-C Bond Formation h(i)ln 2 h(i)ln Tf h(i)ln -Tf h(i)ln h(iii)()2ln Jang,.; Krische, M. J. Am. Chem. Soc. 2004, 126,
51 xidative Cyclization Catalytic chanism egio-etermining C-C Bond Formation Precedes C- Bond Formation h(iii)ln 2 h(i)ln Tf h(i)ln h(i)ln -Tf h(iii)()2ln 2 Jang,.; Krische, M. J. Am. Chem. Soc. 2004, 126,
52 - Cross-ver xperiments ydrometallative Intermediate xidative Cyclization Intermediate h(c)2tf rac-binap C, 25 oc, 2-3 hr t 2 A h(c)2tf rac-binap C, 25 oc, 2-3 hr 2 and 2 or hiiiln hiiiln C3 TsN C3 C3 B 5 mol% Catalyst Loading = NTs, 52% Yield (42% Alkyne eduction) =, 60% Yield TsN Cycloisomerization Without euterium Incorporation 100 mol% Catalyst Loading = NTs, 45% Yield (8% Alkyne eduction) =, 71% Yield TsN TsN 1 2/2, 95% Yield 1 : 2 : 3& : 19.5 : 0.4 TsN 2 TsN 3 4, 88% Yield 1 : 2 : 3&4 3.0 : 0.5 : 96.5 Jang,.; ughes, F.; Gong,.; Zhang, J.; Brodbelt, J.; Krische, M. J. Am. Chem. Soc. 2005, 127,
53 xidative Cyclization with eterolytic 2 Activation 2/2, 95% Yield 1 : 2 : 3& : 19.5 : 0.4 TsN TsN h(iii)ln TsN 1, 88% Yield 1 : 2 : 3&4 3.0 : 0.5 : 96.5 TsN 2 Lnh(I) 2 - Lnh(I) TsN h(iii)()2ln TsN 3 TsN 4 h(iii)ln TsN TsN 2
54 xidative Cyclization with omolytic 2 Activation 2/2, 95% Yield 1 : 2 : 3& : 19.5 : 0.4 TsN TsN h(iii)ln TsN 1, 88% Yield 1 : 2 : 3&4 3.0 : 0.5 : 96.5 TsN 2 Lnh(I) TsN TsN h(iii)ln TsN 3 TsN 4 h(iii)ln TsN 2
55 ydrogen-diated C-C Bond Formation omolytic activation of 2 MLn MLn 1 2 C- reductive elimination Conventional reduction LnM 2 (1atm) 2 M (cat) eterolytic activation of 2 MLn MLn MLn (-, base) MLn C-C bond formation 2 omolytic activation of MLn LnM MLn Jang,.; Krische, M. Acc. Chem. es. 2004, 37,
56 Conclusions Transition-metal catalysis allows access to typically synthetically challenging reactions Choice of terminal reductant offers opportunity for reaction modification eductive hydrogenation has been transformed into an effective C-C bond forming reaction Understanding reaction mechanisms can help expand the scope of transition metal catalyzed reductive couplings
57 Acknowledgments r. Baker r. Smith r. dom r. Wagner Group mbers: Bao, J, Feng, Jon, Leslie, Ping, Qin, Sampa, uwei, and Ying Nicki
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