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Palladium-Catalyzed Tsuji-Trost Allylation of J-Borylated Allyl Acetates

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Palladium-Catalyzed Tsuji-Trost Allylation of J-Borylated Allyl Acetates ANNÉE 2013 THÈSE / UNIVERSITÉ DE RENNES 1 sous le sceau de l’Université Européenne de Bretagne pour le grade de DOCTEUR DE L’UNIVERSITÉ DE RENNES 1 Mention : CHIMIE Ecole doctorale Sciences de la Matière de Rennes présentée par Krishna Kishore Kukkadapu UMR 6510 CNRS Chimie et Photonique Moléculaires UFR Sciences et Propriétés de la Matière Thèse soutenue à Rennes Gamma-borylated le Jeudi 6 juin 2013 allylic acetates as 3 devant le jury composé de : Véronique BELLOSTA carbon functionalized Professeur –ESPCI / rapporteur units : synthesis and Stéphane PELLET-ROSTAING Chargé de recherche CNRS à l’ICSM-CEA / applications rapporteur Florence MONGIN Professeur à l’Université de Renne1 / / examinateur Mathieu PUCHEAULT Chargé de recherche CNRS / examinateur Michel VAULTIER Directeur de recherche CNRS/ / directeur de thèse 1 Table of contents : Résumé de la thèse en français 5 Acknowledgements: 22 Abbreviations: 24 General Introduction: 27 PART ͲA 30 Chapter I: Bibliography 30 I. 1. Synthesis &applications of JͲborylated allylic electrophiles: 31 I. 1. i. Synthesis of JͲborylated allylic electrophiles: 31 I. 1. ii. Applications of JͲborylated allylic electrophiles: 33 I. 1. ii. a. In iridium catalysis: 33 I. 1. ii. b. In copper catalysis: 37 I. 1. ii. c. In palladium catalysis: 39 I. 1. ii. d. In Grignard reaction: 41 I. 1. ii. e. In Diels Alder reaction: 42 I. 1. ii. f. In Mitsunobu reaction: 43 I. 1. ii. g. In cyclopropane synthesis: 46 I. 2. Tsuji ͲTrost Allylation: 48 I. 2. i. Stereochemistry in Tsuji ͲTrost allylation: 51 I. 2. ii. Regioselectivity in Tsuji ͲTrost allylation: 52 I. 2. iii. Asymmetric allylic alkylation (AAA): 54 2 I. 2. iv. Application in natural product synthesis: 58 I. 3. Selectivity issues in palladium catalyzed Tsuji ͲTrost allylation of JͲborylated allyl 61 acetates: Objectives: 62 Chapter II: Palladium catalyzed Tsuji ͲTrost allylation of JͲborylated allyl acetates 64 II. 1. Synthesis of JͲborylated allyl acetates: 65 II. 2. Reactivity of JͲborylated allyl acetates under palladium catalysis: 67 II. 2. i. Regioselectivity with carbon nucleophiles: 69 II. 2. ii. One pot allylation followed by Suzuki ͲMiyaura cross coupling: 72 II. 2. iii. Application of aone Ͳpot strategy: 74 II. 2. iv. Stereoselectivity: 74 II. 2. v. Regioselectivity with nitrogen nucleophiles: 79 II. 2. vi. One Ͳpot allylation followed by Suzuki ͲMiyaura cross coupling: 83 II. 2. vii. Stereoselectivity: 84 II. 3. Some failure attempts in order to use JͲborylated allylic derivatives: 87 Conclusion: 90 Chapter III: Chemo enzymatic resolution of JͲborylated allylic alcohols in continuous 91 flow systems using ionic liquids &sc CO 2 Introduction: 92 III. 1. Ionic liquids as solvents in Green biocatalysis: 92 III.2. Green biocatalysis in super critical carbon dioxide (sc CO 2): 93 III. 3. Literature data on the mechanism of resolution using Candida Antartica Lipase : 94 3 III. 4. Kinetic resolution of JͲborylated allylic alcohols in ionic liquids: 96 III. 5. Enzyme activity in Ionic liquids: 98 III. 6. Optimization of kinetic resolution: 100 III.7. Effect of water in kinetic resolution: 102 III.8. Recyclability of ionic liquids: 102 III. 9. Kinetic resolution using continuous flow systems: 103 III. 10. Results and discussion: 104 Conclusion: 107 PART ͲB: Experimental part 108 Compounds synthesized 171 Conclusions and Perspectives 173 4 6 Juin 2013 Thèse présentée par Mr Krishna Kishore Kukkadapu Pour l'obtention du grade de Docteur de l'Université de Rennes 1 Résumé de la thèse en français Introduction générale: Les boranes vinyliques, les acides boroniques vinyliques et les boronates vinyliques sont des organoboranes où la différence d'électronégativité entre le carbone et le bore est très faible [C (2.55)-B (2.04)] et la liaison entre ces deux atomes est donc peu polaire. Les propriétés caractéristiques du bore permettent de réaliser une grande variété de réactions dans différentes conditions. Beaucoup de groupes de recherche ont exploré les applications synthétiques des organoboranes en synthèse organique. Par exemple les boranes vinyliques peuvent être transformés en les alcènes correspondants par protonolyse, 1 ils peuvent être facilement oxydés avec H 2O2 en présence de base (addition d'un groupe hydroxyle sur la double liaison) pour donner des produits cis-anti Markovnikov. 2 Ils peuvent aussi subir des réactions d'addition pour donner des alcools allyliques, 3 ou des cycloadditions [4+2] pour former deux nouvelles liaisons carbone- carbone via des réactions de Diels-Alder. 4 Les acides 1Brown, H. C.; Zweifel, G. J. Am. Chem. Soc. 1961, 83 , 3834. 2Brown, H. C.; Liotta, R. J. Am. Chem. Soc. , 1979, 101, 96. 3a) Jacob, P.; Brown, H. C. J. Am. Chem. Soc. 1976, 98 , 7832. b) Jacob, P.; Brown, H. C. J. Org. Chem. 1977, 42 , 579. 4a) Matteson, D. S.; Waldbillig, J. O. J. Org. Chem. 1963 , 28 , 366. b) Singleton, D. A.; Martinez, J. P. J. Am. Chem. Soc. 1990, 112, 7423. c) Vaultier, M.; Truchet, F.; Carboni, B. Tetrahedron Lett. 1987, 28 , 4169. 5 vinylboroniques peuvent être transformés en halogénures vinyliques via une halogénolyse, 5 réagir via une réaction de cyclisation radicalaire utilisant la méthode catalytique de Corey en présence d'un initiateur de réaction radicalaire pour obtenir des diols 1,3- ou 1,4. 6 Ils peuvent participer à des réactions de couplage au palladium de type Suzuki pour former de nouvelles liaisons carbone-carbone. 7 Ils peuvent réagir avec des anhydrides pour donner différentes 8 9 cétones DE -insaturatées via des catalyses au palladium ou au rhodium. Les acides vinylboroniques ont aussi été utilisés pour la formation de nouvelles liaisons carbone-azote, 10 carbone-oxygène, 11 carbone-fluor 12 via des réactions catalysées au palladium ou au cuivre. Les boronates vinyliques ont été employés pour former de nouvelles liaisons carbone-carbone via des couplages de Suzuki- Miyaura. Ils sont employés dans la réaction multicomposant de Petasis 13 pour donner des hétérocycles azotés fonctionnalisés. Ils participent aux réactions de métathèse croisée pour donner des boronates vinyliques hautement fonctionnalisés, 14 ils réagissent facilement avec des carbènes générés à partir de diazos pour donner des cyclopropanes 15 et ceci à travers des catalyses au palladium et au rhodium. Les boronates vinyliques, en réaction avec des oxides de nitrile subissent des réactions de cycloaddition 1,3- dipolaire pour donner des isoxazoles. 16 5Brown, H. C.; Campbell, J. B. J. Org. Chem. 1980 , 45 , 389. 6Batey, R. A.; Smil, D. V. J. Angew. Chem. Int. Ed. 1999, 38 , 1798. 7Suzuki, A.; Miyaura, N. Chem. Rev . 1995, 95 , 2457. 8Yamamoto, A.; Ryuki, K.; Shimizu, I. Helvetica Chimica Acta . 2001, 84 , 2996. 9Frost, C. G.; Wadsworth, K. J. Chem. Commun. 2001, 2316. 10 Tao, C-Z.; Xin, C.; Juan, L.; Guo, Q-X. Tetrahedron Letters. 2007, 48 , 3525. 11 Lam, P. Y. S.; Vincent, G.; Clark, C. G.; Deudon, S.; Jadhav, P. K. Tetrahedron Lett. 2001, 42 , 3415. 12 Takeru, F.; Tobias, R. Org. Lett . 2009 , 11 , 2860. 13 a) Petasis, N. A.; Zavialov, I. A. J. Am. Chem. Soc. 1977, 119, 445. b) Batey, R. A.; Mackay, D. B.; Santhakumar, V. J. Am. Chem. Soc. 1999, 121, 5075. 14 a) Morril, C. ; Grubbs, R. H. J. Org. Chem . 2003 , 68 , 6031. b) McNulty, L.; Wright. Z. J. Org. Chem. 2010, 75 , 6001. 15 a) Fontani, P.; Carboni, M.; Vaultier, M. Tetrahedron Lett. 1989, 30 , 4815. b) Toshiro, I.; Hiroshi, M.; Shinya, N. J. Org. Chem. 1990, 55, 4986. c) Yasutaka, F.; Hideki, A. Org. Lett . 2008, 10 , 769. 16 Bianchi, G.; Cogoli, A.; Grünanger, P. J. Organomet. Chem. 1966, 6, 598. 6 Les boronates vinyliques ont aussi été utilisés comme nucléophiles en réaction d'allylation 17 avec catalyse au cuivre ou au palladium. Les transformations précédentes des organoboranes fournissent des précurseurs importants pour la synthèse totale de molécules bioactives complexes qui ont été utilisées dans les domaines de la médecine, de l'agrochimie, des composés pharmaceutiques et de la chimie fine. Les organoboranes peuvent être synthétisés facilement et ceci les rend particulièrement précieux comme intermediaires clés en synthèse organique. Ils peuvent être obtenus par hydroboration d'alcynes à partir d'alkylboranes. 18 Les acides boroniques vinyliques peuvent être synthétisés par une hydroboration d'alcynes avec des alkoxyboranes, suivie d'hydrolyse. 19 Les boronates vinyliques ont été obtenus via des réactifs organométalliques par transmétallation avec le trimethylorthoborate, 20 ou par hydroboration d'alcynes avec des alkoxyboranes. L'introduction d'une substitution en position allylique sur des boronates vinyliques leur confère un degré élevé de flexibilité vis-à-vis des applications en synthèse organique. De tels boronates vinyliques J-substitués possèdent plusieurs sites réactionnels ce qui permet de les considérer comme des substrats difficiles en ce qui concerne la sélectivité des réactions (spécialement vis-à-vis des réactions catalysées par les métaux. 21 Peu de groupes de recherche ont exploré les applications de dérivés vinyl boroniques J-substitués en synthèse organique via des réactions de Grignard, Mitsunobu, Diels-Alder, ainsi que des cyclopropanations asymétriques et des réactions catalysées par des métaux de transition. 17 a) Whittaker, A. M.; Richard, P. R.; Lalic, G. Org. Lett. 2010, 12 , 3216. b) Ortar, G. Tetrahedron Lett. 2003 , 44 , 4311. 18 a) Brown, H. C.; Zweifel, G. J. Am. Chem. Soc . 1961, 83 , 3834. b) Brown, H. C.; Moerikofer, A. W. ibid , 1963, 85 , 2063. 19 Shyam, K. G.; Brown, H. C. ibid , 1975, 97 , 5249. 20 Miyaura, N.; Suzuki, A. Chem. Rev . 1995, 95 , 2457. 21 Carosi, L.; Hall, D. G. Angew. Chem. Int. Ed. 2007, 46 , 5913. 7 Différentes méthodes ont été employées pour leur préparation à partir de J-céto vinylboronates par réduction avec des hydrures ou des dérivés du zinc, 22 par hydroboration d'alcools propargyliques avec soit le pinacol borane ou le di-isopinocamphenyl borane suivie par une refonctionnalisation dans ce dernier cas.
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