Effective synthesis of bicyclodienes via palladium-catalyzed asymmetric allylic alkylation and ruthenium-catalyzed cycloisomerization

[n.3.0]Bicycles (n = 3–6) can be synthesized using palladium-catalyzed asymmetric allylic alkylation followed by rutheniumcatalyzed cycloisomerization. New types of triarylphosphino-1,2-diaminooxazoline ligands show the same high levels of enantioselectivity observed with Trost ligand when employed in Pd-catalyzed allylic alkylation reactions. The enyne products of these allylic alkylation reactions were further elaborated using a Ru-catalyzed redox isomerization process, for which a mechanism is proposed.

PDF

___

1. Weintraub PM, Sabol JS, Kane JM, Borcherding DR. Recent advances in the synthesis of piperidones and piperidines. Tetrahedron 2003; 59 (17): 2953-2989. doi: 10.1016/S0040-4020(03)00295-3.
2. Dörrwald ZF. Metal Carbenes in Organic Synthesis.Hoboken, NJ, USA: Wiley-VCH, 2008.
3. Barluenga J, Rodríguez F, Fañanás FJ, Flórez J. Cycloaddition Reactions of Group 6 Fischer Carbene Complexes. In: Metal Carbenes in Organic Synthesis. Topics in Organometallic Chemistry. Berlin, Heidelberg, Germany: Springer Berlin Heidelberg, 2004: pp. 59-121.
4. Trost BM, Lautens M. Cyclization via isomerization: a palladium(2+)-catalyzed carbocyclization of 1,6-enynes to 1,3- and 1,4-dienes. Journal of the American Chemical Society 1985; 107 (6): 1781-1783. doi: 10.1021/ja00292a065.
5. Trost BM, Verhoeven TR. Allylic alkylation. Palladium-catalyzed substitutions of allylic carboxylates.Stereo- and regiochemistry. Journal of the American Chemical Society 1980; 102 (14): 4730-4743. doi: 10.1021/ja00534a029.
6. Trost BM, Bunt RC. Asymmetric induction in allylicalkylations of 3-(acyloxy)cycloalkenes. Journal of the American Chemical Society 1994; 116 (9): 4089-4090. doi: 10.1021/ja00088a059.
7. Trost BM, Organ MG, O’Doherty GA. Asymmetric synthesis of allylicsulfones useful as asymmetric building blocks. Journal of the American Chemical Society 1995; 117 (38): 9662-9670. doi: 10.1021/ja00143a007.
8. Trost BM, Stenkamp D, Pulley SR. An Enantioselective Synthesis ofcis-4-tert-Butoxycarbamoyl-1-methoxycarbonyl-2-cyclopentene—A Useful, General Building Block. Chemistry - A European Journal 1995; 1 (8): 568-572. doi: 10.1002/chem.19950010812.
9. Trost BM. The atom economy--a search for synthetic efficiency. Science (New York, N.Y.) 1991; 254 (5037): 1471-1477. doi: 10.1126/ science.1962206.
10. Trost BM. Atom Economy—A Challenge for Organic Synthesis: Homogeneous Catalysis Leads the Way. Angewandte Chemie International Edition in English 1995; 34 (3): 259-281. doi: 10.1002/anie.199502591.
11. Trost BM, Dyker G, Kulawiec RJ. A ruthenium-catalyzed reconstitutive condensation of acetylenes and allyl alcohols. Journal of the American Chemical Society 1990; 112 (21): 7809-7811. doi: 10.1021/ja00177a059.
12. Trost BM, Kulawiec RJ. Mechanism of the ruthenium-catalyzed reconstitutive condensation of allylic alcohols and terminal alkynes. Journal of the American Chemical Society 1992; 114 (14): 5579-5584. doi: 10.1021/ja00040a015.
13. Trost BM, Kulawiec RJ, Hammes A. Ruthenium catalyzed reconstitutive condensation. Application to functionalized steroid side chains. Tetrahedron Letters 1993; 34 (4): 587-590. doi: 10.1016/S0040-4039(00)61626-X.
14. Trost BM, Flygare JA. A Practical Synthesis of Rosefuran.Furans from Acetylenes and Allyl Alcohols. The Journal of Organic Chemistry 1994; 59 (5): 1078-1082. doi: 10.1021/jo00084a026.
15. Trost BM, Rhee YH. Ruthenium-Catalyzed Cycloisomerization−Oxidation of Homopropargyl Alcohols. A New Access to γ-Butyrolactones. Journal of the American Chemical Society 1999; 121 (50): 11680-11683. doi: 10.1021/ja992013m.
16. Trost BM, Rhee YH. A Ru catalyzed divergence: oxidative cyclization vscycloisomerization of bis-homopropargylic alcohols. Journal of the American Chemical Society 2002; 124 (11): 2528-2533. doi: 10.1021/ja011840w.
17. Trost BM, Martinez JA, Kulawiec RJ, Indolese AF. Ruthenium-catalyzed addition of allyl alcohols and acetylenes. A simple synthesis of .gamma.,.delta.-unsaturated ketones. Journal of the American Chemical Society 1993; 115 (22): 10402-10403. doi: 10.1021/ja00075a083.
18. Trost BM, Indolese A. Ruthenium-catalyzed addition of alkenes to acetylenes. Journal of the American Chemical Society 1993; 115 (10): 4361-4362. doi: 10.1021/ja00063a064.
19. Trost BM, Imi K, Indolese AF. 1,5-Cyclooctadiene as a bis-homodiene partner in a metal-catalyzed [4 + 2]cycloaddition. Journal of the American Chemical Society 1993; 115 (19): 8831-8832. doi: 10.1021/ja00072a043.
20. Trost BM, Probst GD, Schoop A. Ruthenium-Catalyzed Alder Ene Type Reactions. A Formal Synthesis of Alternaric Acid. Journal of the American Chemical Society 1998; 120 (36): 9228-9236. doi: 10.1021/ja981540n.
21. Trost BM, Pinkerton AB, Toste FD, Sperrle M. Synthesis of 1,1-disubstituted alkenes via a Ru-catalyzed addition. Journal of the American Chemical Society 2001; 123 (50): 12504-12509. doi: 10.1021/ja012009m.
22. Trost BM, Shen HC, Pinkerton AB. A Synthesis of Trisubstituted Alkenes by a Ru-Catalyzed Addition. Chemistry - A European Journal 2002; 8 (10): 2341. doi: 10.1002/1521-3765(20020517)8:10<2341::AID-CHEM2341>3.0.CO;2-A
23. Trost BM, Gunzner JL. Total synthesis of deschlorocallipeltoside A. Journal of the American Chemical Society 2001; 123 (38): 9449-9450. doi: 10.1021/ja011424b.
24. Trost BM, Gunzner JL, Dirat O, Rhee YH. Callipeltoside a: total synthesis, assignment of the absolute and relative configuration, and evaluation of synthetic analogues. Journal of the American Chemical Society 2002; 124 (35): 10396-10415. doi: 10.1021/ja0205232.
25. Trost BM, Chisholm JD, Wrobleski ST, Jung M. Ruthenium-catalyzed alkene-alkyne coupling: synthesis of the proposed structure of amphidinolide A. Journal of the American Chemical Society 2002; 124 (42): 12420-12421. doi: 10.1021/ja027883+.
26. Trost BM. Centenary Lecture. Cyclopentanoids: a challenge for new methodology. Chemical Society Reviews 1982; 11 (2): 141. doi: 10.1039/CS9821100141.
27. Trost BM, Machacek MR, Ball ZT. Ruthenium-catalyzed vinylsilane synthesis and cross-coupling as a selective approach to alkenes: benzyldimethylsilyl as a robustvinylmetal functionality. Organic letters 2003; 5 (11): 1895-1898. doi: 10.1021/ol034463w.
28. Trost BM, Machacek MR. An efficient one-pot enantio- and diastereoselective synthesis of heterocycles. Angewandte Chemie (International ed. in English) 2002; 41 (24): 4693-4697. doi: 10.1002/anie.200290019.
29. Trost BM, Yang H, Probst GD. A formal synthesis of (-)-mycalamide A. Journal of the American Chemical Society 2004; 126 (1): 48-49. doi: 10.1021/ja038787r.
30. Trost BM, Pinkerton AB. A Ruthenium-Catalyzed Two-Component Addition To Form 1,3-Dienes. Journal of the American Chemical Society 1999; 121 (16): 4068-4069. doi: 10.1021/ja990291f.
31. Trost BM, Pinkerton AB, Seidel M. Ruthenium-catalyzed two-component addition to form 1,3-dienes: optimization, scope, applications, and mechanism. Journal of the American Chemical Society 2001; 123 (50): 12466-12476. doi: 10.1021/ja011428g.
32. Clark JL, Duckett SB. Photochemical studies of (η5-C5H5)Ru(PPh3)2Cl and (η5-C5H5)Ru(PPh3)2Me: formation of Si-H and C-H bond activation products. Dalton transactions (Cambridge, England : 2003) 2014; 43 (3): 1162-1171. doi: 10.1039/C3DT52069B.
33. Trost BM, Older CM. A Convenient Synthetic Route to [CpRu(CH 3 CN) 3 ]PF 6. Organometallics 2002; 21 (12): 2544-2546. doi: 10.1021/ om020143p.
34. Trost BM, Frederiksen MU, Rudd MT. Ruthenium-catalyzed reactions--a treasure trove of atom-economic transformations. AngewandteChemie (International ed. in English) 2005; 44 (41): 6630-6666. doi: 10.1002/anie.200500136.
35. Trost BM, Ryan MC, Rao M. Chiral cyclopentadienylrutheniumsulfoxide catalysts for asymmetric redox bicycloisomerization. Beilstein journal of organic chemistry 2016; 12: 1136-1152.doi: 10.3762/bjoc.12.110.
36. Trost BM, Toste FD. Mechanistic dichotomy in CpRu(CH(3)CN)(3)PF(6) catalyzed enynecycloisomerizations. Journal of the American Chemical Society 2002; 124 (18): 5025-5036. doi: 10.1021/ja012450c.
37. Trost BM, Ferreira EM, Gutierrez AC. Ruthenium- and palladium-catalyzed enynecycloisomerizations: differentially stereoselective syntheses of bicyclic structures. Journal of the American Chemical Society 2008; 130 (48): 16176-16177. doi: 10.1021/ja8078835.
38. Piera J, Persson A, Caldentey X, Bäckvall J-E. Water as nucleophile in palladium-catalyzed oxidative carbohydroxylation of allenesubstituted conjugated dienes. Journal of the American Chemical Society 2007; 129 (46): 14120-14121. doi: 10.1021/ja075488j.
39. Franzén J, Bäckvall J-E. Carbon-carbon bond formation in palladium(II)-catalyzed allylic oxidation: a novel oxidative carbocyclization of allene-substituted olefins. Journal of the American Chemical Society 2003; 125 (20): 6056-6057. doi: 10.1021/ja029505a.
40. Löfstedt J, Närhi K, Dorange I, Bäckvall J-E. Palladium-catalyzed carbocyclization of allene-diene derivatives.Exploring different nucleophiles. The Journal of Organic Chemistry 2003; 68 (19): 7243-7248. doi: 10.1021/jo034412c.
41. Dorange I, Löfstedt J, Närhi K, Franzén J, Bäckvall J-E. Allenes as carbon nucleophiles in intramolecular attack on (pi-1,3-diene)palladium complexes: evidence for trans carbopalladation of the 1,3-diene. Chemistry - A European Journal 2003; 9 (14): 3445-3449. doi: 10.1002/ chem.200305056.
42. Löfstedt J, Franzén J, Bäckvall JE. Carbon-carbon bond formation in regio- and stereoselective palladium-catalyzed cyclization of allenesubstituted conjugated dienes. The Journal of Organic Chemistry 2001; 66 (24): 8015-8025. doi: 10.1021/jo0157324.
43. Piera J, Närhi K, Bäckvall J-E. PdII-catalyzed aerobic allylic oxidative carbocyclization of allene-substituted olefins: immobilization of an oxygen-activating catalyst. Angewandte Chemie (International ed. in English) 2006; 45 (41): 6914-6917. doi: 10.1002/anie.200602421.
44. Franzén J, Löfstedt J, Dorange I, Bäckvall J-E. Allenes as carbon nucleophiles in palladium-catalyzed reactions: observation of anti attack of allenes on (pi-allyl)palladium complexes. Journal of the American Chemical Society 2002; 124 (38): 11246-11247. doi: 10.1021/ ja026150m.
45. Johnston EV, Karlsson EA, Lindberg SA, Akermark B, Bäckvall J-E. Efficient reoxidation of palladium by a hybrid catalyst in aerobic palladium-catalyzed carbocyclization of enallenes. Chemistry - A European Journal 2009; 15 (28): 6799-6801. doi: 10.1002/ chem.200900980.
46. Trost BM. The 2014 Tetrahedron Prize for Creativity in Organic Chemistry. Palladium and Other Transition Metal-Catalyzed Reactions: Methods and Applications. Tetrahedron 2015; 71 (35): 5707. doi: 10.1016/j.tet.2015.06.043.
47. Trost BM, Fleming I. Comprehensive organic synthesis: Selectivity, strategy & efficiency in modern organic chemistry, Vol. 7. Oxford, UK: Pergamon Press, 1991.
48. Trost BM, Gutierrez AC, Ferreira EM. Differential reactivities of enyne substrates in ruthenium- and palladium-catalyzed cycloisomerizations. Journal of the American Chemical Society 2010; 132 (26): 9206-9218. doi: 10.1021/ja103663h.
49. Campbell MJ, Pohlhaus PD, Min G, Ohmatsu K, Johnson JS. An “anti-Baldwin” 3-exo-dig cyclization: preparation of vinylidenecyclopropanes from electron-poor alkenes. Journal of the American Chemical Society 2008; 130 (29): 9180-9181. doi: 10.1021/ja803553a.
50. Trost BM, Breit B, Peukert S, Zambrano J, Ziller JW. A New Platform for Designing Ligands for Asymmetric Induction in AllylicAlkylations. AngewandteChemie International Edition in English 1995; 34 (21): 2386-2388. doi: 10.1002/anie.199523861.
51. Huang D, Liu X, Li L, Cai Y, Liu W. et al. Enantioselectivebromoaminocyclization of allyl N-tosylcarbamates catalyzed by a chiral phosphine-Sc(OTf)3 complex. Journal of the American Chemical Society 2013; 135 (22): 8101-8104. doi: 10.1021/ja4010877.
52. Myers EL, Raines RT. Inside Cover: A Phosphine-Mediated Conversion of Azides into Diazo Compounds AngewandteChemie (International ed. in English) 2009; 48 (13): 2246. doi: 10.1002/anie.200990061.
53. Coffinier R, El Assal M, Peixoto PA, Bosset C, Miqueu K. et al. Total Synthesis of (-)-Bacchopetiolone via an Asymmetric Hydroxylative Phenol Dearomatization/4+2-Dimerization Cascade Promoted by a Novel Salen-Type Chiral Iodane. Organic letters 2016; 18 (5): 1120- 1123. doi: 10.1021/acs.orglett.6b00224.
54. Glorius F, Neuburger M, Pfaltz A. Highly Enantio- and RegioselectiveAllylicAlkylations Catalyzed by Chiral [Bis(dihydrooxazole)] molybdenum Complexes. Helvetica ChimicaActa 2001; 84 (10): 3178-3196. doi: 10.1002/1522-2675(20011017)84:10<3178::AIDHLCA3178>3.0.CO;2-Q.
55. Glorius F, Pfaltz A. Enantioselective Molybdenum-Catalyzed Allylic Alkylation Using Chiral Bisoxazoline Ligands. Organic letters 1999; 1 (1): 141-144. doi: 10.1021/ol990602r.
56. Kusama H, Watanabe E, Ishida K, Iwasawa N. Efficient control for the cationic platinum(II)-catalyzed concise synthesis of two types of fused carbocycles with angular oxygen functionality. Chemistry, an Asian journal 2011; 6 (9): 2273-2277. doi: 10.1002/asia.201100460.
57. Hernández A-I, Balzarini J, Karlsson A, Camarasa M-J, Pérez-Pérez M-J. Acyclic nucleoside analogues as novel inhibitors of human mitochondrial thymidine kinase. Journal of medicinal chemistry 2002; 45 (19): 4254-4263. doi: 10.1021/jm011128+.
58. Trost, BM, Schultz JE. Palladium-catalyzed asymmetric allylic alkylation strategies for the synthesis of acyclic tetrasubstitutedstereocenters. Synthesis 2019; 51 (01): 1-30. doi: 10.1055/s-0037-1610386.
59. Trost, BM. Pd- and Mo-catalyzed asymmetric allylic alkylation. Organic Process Research & Development. 2012; 16 (2): 185-194. doi: 10.1021/op200294r.
60. Trost BM, Toste FD. Regio- and enantioselectiveallylic alkylation of an unsymmetrical substrate: a working model. Journal of the American Chemical Society 1999; 121 (19): 4545-4554. doi: 10.1021/ja9828713.
61. Butts CP, Filali E, Lloyd-Jones GC, Norrby P-O. et al. Structure-based rationale for selectivity in the asymmetric allylic alkylation of cycloalkenyl esters employing the Trost ‘Standard Ligand’ (TSL): isolation, analysis and alkylation of the monomeric form of the cationic η3-cyclohexenyl complex [(η3-c-C6H9)Pd(TSL)]+. Journal of the American Chemical Society 2009; 131 (29): 9945-9957. doi: 10.1021/ ja8099757.
62. Craig PB, Emane F, Guy CL-J, Per-Ola N, David AS. et al. CuI‐catalysedenantioselective alkyl 1,4‐additions to (E)‐Nitroalkenes and cyclic enones with phosphino‐oxazoline ligands. European Journal of Organic Chemistry 2018; 24 (12): 3122-3130. doi: 10.1002/ejoc.201800476.
63. Trost BM, Franz AW. Ruthenium-catalyzed domino redox bicycloisomerization.An atom-economical synthesis of 3.1.0- and 4.1.0carboand heterocycles. Journal of the American Chemical Society 2010; 132 (51): 18429. doi: 10.1021/ja1088452.
64. Sabitha G, Venkata Reddy E, Swapna R, Mallikarjun Reddy N, Yadav JS. Bismuth(III) Chloride Catalyzed Efficient and Selective Cleavage of Trityl Ethers. Synlett 2004; (7): 1276-1278. doi: 10.1055/s-2004-825602.
65. Copéret C, Ma S, Sugihara T, Negishi E-i. Cyclic carbopalladation of alkynes terminated by carbonylativeamidation. Tetrahedron 1996; 52 (35): 11529-11544. doi: 10.1016/0040-4020(96)00640-0.
66. Södergren MJ, Andersson PG. Chiral, bicyclic proline derivatives and their application as ligands for copper in the catalytic asymmetric allylic oxidation of olefins. Tetrahedron Letters 1996; 37 (42): 7577-7580. doi: 10.1016/0040-4039(96)01664-4.
67. Tran BL, Driess M, Hartwig JF. Copper-catalyzed oxidative dehydrogenative carboxylation of unactivated alkanes to allylic esters via alkenes. Journal of the American Chemical Society 2014; 136 (49): 17292-17301. doi: 10.1021/ja510093x.
68. Matsuyama K, Inoue T, Inoue Y. Self-Sensitized Diastereodifferentiating Z - E Photoisomerization of 3-, 4-, and 5-Benzoyloxycyclooctenes: Intra- versus Intermolecular Photosensitization. Synthesis 2001; 112 (08): 1167-1174. doi: 10.1055/s-2001-15062.
69. Trost BM, Malhotra S, Olson DE, Maruniak A, Du Bois J. Asymmetric synthesis of diamine derivatives via sequential palladium and rhodium catalysis. Journal of the American Chemical Society 2009; 131 (12): 4190-4191. doi: 10.1021/ja809697p.
70. Sankar U, Mahalakshmi S, Balasubramanian K. A One-Pot Stereoselective Synthesis of Electron-Deficient 4-Substituted (E,E)- 1-Arylsulfonylbuta-1,3-dienes and Their Chemoselective [3+2] Cycloaddition with AzomethineYlides - A Simple Synthesis of 1,3,4-Trisubstituted Pyrrolidines and Pyrroles. Synlett 2013; 24 (12): 1533-1540. doi: 10.1055/s-0033-1339181.
71. Kang T, Kim W-Y, Yoon Y, Kim BG, Lee H-Y. Tandem cycloaddition reactions of allenyldiazo compounds forming triquinanes via trimethylenemethanediyls. Journal of the American Chemical Society 2011; 133 (45): 18050-18053. doi: 10.1021/ja207591e.