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Synlett 2016; 27(16): 2396-2400
DOI: 10.1055/s-0035-1562508
DOI: 10.1055/s-0035-1562508
letter
γ-Lactone Synthesis via Palladium(II)-Catalyzed Lactonization of Unactivated Methylene C(sp3)–H Bonds
Weitere Informationen
Publikationsverlauf
Received: 09. Mai 2016
Accepted after revision: 31. Mai 2016
Publikationsdatum:
08. Juli 2016 (online)
Abstract
A palladium(II)-catalyzed intramolecular lactonization of unactivated methylene C(sp3)–H bonds using PIP bidentate auxiliary is described. This method provides an efficient and concise pathway to synthesize functionalized γ-lactones.
Key words
palladium - bidentate auxiliary - C(sp3)–H activation - lactonization - methylene - intramolecularSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1562508.
- Supporting Information
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References and Notes
- 1a Hoffman HM. R, Rabe J. Angew. Chem., Int. Ed. Engl. 1985; 24: 94
- 1b Seitz M, Reiser O. Curr. Opin. Chem. Biol. 2005; 9: 285
- 1c Natural Lactones and Lactams: Synthesis, Occurrence and Biological Activity. Janecki T. Wiley-VCH; Weinheim: 2013
- 3a Gutekunst WR, Baran PS. Chem. Soc. Rev. 2011; 40: 1976
-
3b Baudoin O. Chem. Soc. Rev. 2011; 40: 4902
- 3c Wasa M, Engle KM, Yu J.-Q. Isr. J. Chem. 2010; 50: 605
-
3d Yeung CS, Dong VM. Chem. Rev. 2011; 111: 1215
- 3e Li H, Li B.-J, Shi Z.-J. Catal. Sci. Technol. 2011; 1: 191
-
3f Jazzar R, Hitce J, Renaudat A, Sofack-Kreutzer J, Baudoin O. Chem. Eur. J. 2010; 16: 2654
-
3g Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
- 3h Daugulis O, Do H.-Q, Shabashov D. Acc. Chem. Res. 2009; 42: 1074
- 3i Liu C, Liu D, Lei A. Acc. Chem. Res. 2014; 47: 3459
- 3j Zhang B, Guan H.-X, Liu B, Shi B.-F. Chin. J. Org. Chem. 2014; 34: 1487
- 4a Dick AR, Hull KL, Sanford MS. J. Am. Chem. Soc. 2004; 126: 2300
- 4b Desai LV, Hull KL, Sanford MS. J. Am. Chem. Soc. 2004; 126: 9542
- 4c Giri R, Liang J, Lei JG, Li JJ, Wang DH, Chen X, Naggar IC, Guo C, Foxman BM, Yu J.-Q. Angew. Chem. Int. Ed. 2005; 44: 7420
- 5a Dangel BD, Johnson JA, Sames D. J. Am. Chem. Soc. 2001; 123: 8149
- 5b Lee JM, Chang S. Tetrahedron Lett. 2006; 47: 1375
- 6 Novák P, Correa A, Gallardo-Donaire J, Martin R. Angew. Chem. Int. Ed. 2011; 50: 12236
- 7a Cheng X.-F, Li Y, Yin Y.-M, Su F, Wang J.-Y, Sheng J, Vora HU, Wang X.-S, Yu J.-Q. J. Am. Chem. Soc. 2013; 135: 1236
- 7b Yang M, Jiang X, Shi W, Zhu Q, Shi Z. Org. Lett. 2013; 15: 690
- 7c Li Y, Ding Y.-J, Wang J.-Y, Su Y.-M, Wang X.-S. Org. Lett. 2013; 15: 2574
- 8a Chen F.-J, Zhao S, Hu F, Chen K, Zhang Q, Zhang S.-Q, Shi B.-F. Chem. Sci. 2013; 4: 4187
- 8b Zhang Q, Chen K, Rao W.-H, Zhang Y.-J, Chen F.-J, Shi B.-F. Angew. Chem. Int. Ed. 2013; 52: 13588
- 8c Zhang Q, Yin X.-S, Zhao S, Fang S.-L, Shi B.-F. Chem. Commun. 2014; 50: 8353
- 8d Chen F.-J, Liao G, Li X, Wu J, Shi B.-F. Org. Lett. 2014; 16: 5644
- 8e Yan S.-Y, Liu Y.-J, Liu B, Liu Y.-H, Shi B.-F. Chem. Commun. 2015; 51: 4069
- 8f Dailler D, Danoun G, Baudoin O. Angew. Chem. Int. Ed. 2015; 54: 4919
-
9a Giri R, Maugel N, Li J.-J, Wang D.-H, Breazzano SP, Saunders LB, Yu J.-Q. J. Am. Chem. Soc. 2007; 129: 3510
- 9b Mei T.-S, Giri R, Maugel N, Yu J.-Q. Angew. Chem. Int. Ed. 2008; 47: 5215
- 10a Ma J.-A, Cahard J. J. Fluorine Chem. 2007; 128: 975
- 10b Furuya T, Kamlet AS, Ritter T. Nature (London, U.K.) 2011; 473: 470
- 10c Tomashenko OA, Grushin VV. Chem. Rev. 2011; 111: 4475
- 10d Zhou Y, Wang J, Gu Z, Wang S, Zhu W, Aceña JL, Soloshonok VA, Izawa K, Liu H. Chem. Rev. 2016; 116: 422 ; and references cited therein
- 11a Yoneyama T, Crabtree RH. J. Mol. Catal. A: Chem. 1996; 108: 35
- 11b Neufeldt SR, Sanford MS. Acc. Chem. Res. 2012; 45: 936
- 12a Wang G.-W, Yuan T.-T. J. Org. Chem. 2010; 75: 476
-
12b Li W, Sun P. J. Org. Chem. 2012; 77: 8362
- 12c Jiang T.-S, Wang G.-W. J. Org. Chem. 2012; 77: 9504
- 12d Wang X, Lu Y, Dai H.-X, Yu J.-Q. J. Am. Chem. Soc. 2010; 132: 12203
- 12e Xiao B, Gong T.-J, Liu Z.-J, Liu J.-H, Luo D.-F, Xu J, Liu L. J. Am. Chem. Soc. 2011; 133: 9250
- 13a Muñiz K. Angew. Chem. Int. Ed. 2009; 48: 9412
- 13b Xu L.-M, Li B.-J, Yang Z, Shi Z.-J. Chem. Soc. Rev. 2010; 39: 712
- 13c Powers DC, Ritter T. Acc. Chem. Res. 2012; 45: 840
- 13d Racowski J, Sanford MS. Top. Organomet. Chem. 2011; 53: 61
- 14a Liu G, Stahl SS. J. Am. Chem. Soc. 2006; 128: 7179
- 14b Racowaski JM, Gary JB, Sanford MS. Angew. Chem. Int. Ed. 2012; 51: 3412
- 14c Thompson SJ, Thach DQ, Dong G. J. Am. Chem. Soc. 2015; 137: 11586
- 15 General Procedure for the Lactonization To a 50 mL Schlenk tube was added substrate (0.2 mmol), Pd(OAc)2 (4.5 mg, 0.02 mmol), PhI(OAc)2 (128.8 mg, 0.4 mmol), NaI (30 mg, 0.1 mmol), AgOAc (16.7 mg, 0.1 mmol), and toluene (2 mL). This tube was charged with N2, and the mixture was then heated at 100 °C for 24 h. The reaction mixture was cooled to room temperature, diluted with EtOAc, and quenched with water. The aqueous phase was extracted with EtOAc (3 × 10 mL). The combined organic phase was dried with anhydrous MgSO4. After concentration, purification by flash chromatography gave target products.
- 16 2-(5-Oxotetrahydrofuran-2-yl)-N-[2-(pyridin-2-yl)propan-2-yl]acetamide (2a) The title compound 2a was prepared according to general procedure for the lactonization. Purification by flash chromatography in EtOAc gave the desired product as a white solid in 75% yield. 1H NMR (400 MHz, CDCl3): δ = 8.50 (d, J = 4.4 Hz, 1 H), 7.95 (s, 1 H), 7.72 (td, J = 7.8, 1.8 Hz, 1 H), 7.39 (d, J = 8.1 Hz, 1 H), 7.20 (ddd, J = 7.4, 4.9, 0.9 Hz, 1 H), 4.95 (m, 1 H), 2.75 (dd, J = 14.7, 6.5 Hz, 1 H), 2.63–2.52 (m, 3 H), 2.51–2.40 (m, 1 H), 2.12–1.99 (m, 1 H), 1.75 (s, 3 H), 1.74 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 176.99, 167.87, 164.32, 147.84, 137.45, 122.23, 119.66, 57.02, 43.34, 29.94, 28.93, 27.92, 27.69, 27.66. HRMS (EI-TOF): m/z calcd for C14H18N2O3 [M+]: 262.1317; found: 262.1311
For recent reviews on C(sp3)–H activation, see:
For the development and application of PIP directing group in methylene C(sp3)–H functionalization, see:
For an application of the PIP directing group in total synthesis:
For selected reviews, see:
For selected reviews on high-valent palladium, see: