From Enynyl Esters to Functionalized Polycyclic Derivatives via Cycloisomerization and Post-Functionalization

Dedicated to Jean F. Normant with admiration

Abstract

The post-functionalization of ketone products originating from the PtCl₂-catalyzed cycloisomerization of enynyl esters is described. Post-functionalization is accomplished via diastereoselective alkylation, regioselective cyclopropane opening and regioselective Baeyer–Villiger and Beckmann rearrangements to provide functionalized polycycles.

Key words

cycloisomerization - platinum - enynyl ester - polycyclic ketone - Baeyer–Villiger - Beckmann rearrangement - lactones - lactams

• References


For pioneering discoveries, see:
• 1a Strickler H, Davis JB, Ohloff G. Helv. Chim. Acta 1976; 59: 1328
• 1b Rautenstrauch V. J. Org. Chem. 1984; 49: 950
• 2 Mainetti E, Mouriès V, Fensterbank L, Malacria M, Marco-Contelles J. Angew. Chem. Int. Ed. 2002; 41: 2132
• 3a Fürstner A. Chem. Soc. Rev. 2009; 38: 3208
• 3b Fensterbank L, Malacria M. Acc. Chem. Res. 2014; 47: 953
• 3c Dorel R, Echavarren AM. Chem. Rev. 2015; 115: 9028

For recent reviews on propargyl acetate migrations, see:
• 4a Fensterbank L, Goddard J.-P, Malacria M, Simonneau A In Gold Catalysis: An Homogeneous Approach . Toste FD, Michelet V. Imperial College Press; London: 2014: 331
• 4b Shiroodi RK, Gevorgyan V. Chem. Soc. Rev. 2013; 42: 4991
• 4c Day PD, Chan PW. H. Adv. Synth. Catal. 2016; 358: 1368

For seminal reports, see:
• 5a Mamane V, Gress T, Krause H, Fürstner A. J. Am. Chem. Soc. 2004; 126: 8654
• 5b Johansson MJ, Gorin DJ, Staben ST, Toste FD. J. Am. Chem. Soc. 2005; 127: 18002
• 5c Marion N, de Frémont P, Lemière G, Stevens ED, Fensterbank L, Malacria M, Nolan SP. Chem. Commun. 2006; 2048
• 6a Shu X.-z, Schienebeck CM, Song W, Guzei IA, Tang W. Angew. Chem. Int. Ed. 2013; 52: 13601
• 6b Fukuyama T, Ohta Y, Brancour B, Miyagawa K, Ryu I, Dhimane A.-L, Fensterbank L, Malacria M. Chem. Eur. J. 2012; 18: 7243
• 6c Shu X.-z, Shu D, Schienebeck CM, Tang W. Chem. Soc. Rev. 2012; 41: 7698 ; and references therein
• 7a Amjun S, Marco-Contelles J. Tetrahedron 2005; 61: 4793
• 7b Fürstner A, Hannen P. Chem. Eur. J. 2006; 12: 3006
• 7c Fehr C, Winter B, Magpantay I. Chem. Eur. J. 2009; 15: 9773
• 7d Fehr C, Vuagnoux M, Buzas A, Arpagaus J, Sommer H. Chem. Eur. J. 2011; 17: 6214
• 7e Watson ID. G, Ritter S, Toste FD. J. Am. Chem. Soc. 2009; 131: 2056
• 7f Rao W, Chan PW. H. Chem. Eur. J. 2014; 20: 713
• 8a Cariou K, Mainetti E, Fensterbank L, Malacria M. Tetrahedron 2004; 60: 9745
• 8b Harrak Y, Blaszykowski C, Bernard M, Cariou K, Mainetti E, Mouriès V, Dhimane A.-L, Fensterbank L, Malacria M. J. Am. Chem. Soc. 2004; 126: 8656
• 8c Blaszykowski C, Harrak H, Gonçalves M.-H, Cloarec J.-M, Dhimane A.-L, Fensterbank L, Malacria M. Org. Lett. 2004; 6: 3771
• 8d Moreau X, Goddard J.-P, Bernard M, Lemière G, López-Romero JM, Mainetti E, Marion N, Mouriès V, Thorimbert S, Fensterbank L, Malacria M. Adv. Synth. Catal. 2008; 350: 43
• 8e Moreau X, Hours A, Fensterbank L, Goddard J.-P, Malacria M, Thorimbert S. J. Organomet. Chem. 2009; 694: 561
• 8f Harrak Y, Makhlouf M, Azzaro S, Mainetti E, Lopez Romero JM, Cariou K, Gandon V, Goddard J.-P, Malacria M, Fensterbank L. J. Organomet. Chem. 2011; 696: 388

For mechanistic insights, see:
• 9a Soriano E, Marco-Contelles J. Chem. Eur. J. 2008; 14: 6771
• 9b Marion N, Lemière G, Correa A, Ramon RS, Moreau X, de Frémont P, Dahmane R, Hours A, Lesage D, Tabet J.-C, Goddard J.-P, Gandon V, Cavallo L, Fensterbank L, Malacria M, Nolan SP. Chem. Eur. J. 2009; 15: 3243 ; and refs 7b-d
• 10 Mino T, Masuda S, Nishio M, Yamashita M. J. Org. Chem. 1997; 62: 2633
• 11 CCDC 1481737 (3a-DNPH) and 1481738 (3c-DNPH) contain the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 12 Gordon HL, Freeman S, Hudlicky T. Synlett 2005; 2911
• 13a Di Bello N, Pellacani L, Tardella PA. Synthesis 1978; 227
• 13b See also: Huang H, Forsyth CJ. Tetrahedron 1997; 53: 16341
• 14 Demuth M, Raghavan PR. Helv. Chim. Acta 1979; 62: 2338
• 15 Wiberg KB, Snoonian JR. J. Org. Chem. 1998; 63: 1390
• 16 Under forcing conditions (5 equiv of mCPBA, 3 days reaction time), 50% conversion was observed giving presumably BV products, but not very cleanly.
• 17a Beckmann E. Ber. Dtsch. Chem. Ges. 1886; 19: 988
• 17b Winter DK, Drouin A, Lessard J, Spino C. J. Org. Chem. 2010; 75: 2610
• 17c Guy Donaruma L, Heldt WZ. Org. React. 2011; 11: 1
• 17d Tandon VK, Awasthi AK, Maurya HK, Mishra P. J. Heterocycl. Chem. 2012; 49: 424
• 17e Zhang J, Dong C, Du C, Luo G. Org. Process Res. Dev. 2015; 19: 352
• 18 Kotha S, Ravikumar O, Majhi J. Beilstein J. Org. Chem. 2015; 11: 1503
• 19 CCDC 1481739 (13) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 20 Olah GA, Fung AP. Org. Synth. 1985; 63: 188