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Synlett 2019; 30(15): 1787-1790
DOI: 10.1055/s-0039-1690130
DOI: 10.1055/s-0039-1690130
letter
Rhodium(III)-Catalyzed Cyclopropanation of Unactivated Olefins Initiated by C–H Activation
We thank the National Institute of General Medical Sciences (NIGMS, Grant No. GM80442) for support.Further Information
Publication History
Received: 23 May 2019
Accepted after revision: 11 July 2019
Publication Date:
22 July 2019 (online)
Abstract
We have developed a rhodium(III)-catalyzed cyclopropanation of unactivated olefins initiated by an alkenyl C–H activation. A variety of 1,1-disubstituted olefins undergo efficient cyclopropanation with a slight excess of alkene stoichiometry. A series of mechanistic interrogations implicate a metal carbene as an intermediate.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0039-1690130.
- Supporting Information
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References and Notes
- 1a Chen DY.-K, Pouwer RH, Richard J.-A. Chem. Soc. Rev. 2012; 41: 4631
- 1b Talele TT. J. Med. Chem. 2016; 59: 8712
- 2a Banwell MG, Edwards AJ, Jolliffe KA, Smith JA, Hamel E, Verdier-Pinard P. Org. Biomol. Chem. 2003; 1: 296
- 2b Newhouse TR, Kaib PS. J, Gross AW, Corey EJ. Org. Lett. 2013; 15: 1591
- 3a Doyle MP, Forbes DC. Chem. Rev. 1998; 98: 911
- 3b Davies HM. L, Antoulinakis EG. Org. React. 2004; 57: 1
- 4a Lebel H, Marcoux J.-F, Molinaro C, Charette AB. Chem. Rev. 2003; 103: 977
- 4b Charette AB, Beauchemin A. Org. React. 2004; 58: 1
- 5a Friedrich EC, Biresaw G. J. Org. Chem. 1982; 47: 1615
- 5b Stahl K.-J, Hertzsch W, Musso H. Liebigs Ann. Chem. 1985; 1474
- 5c Roberts C, Walton JC. J. Chem. Soc., Perkin Trans. 2 1985; 841
- 5d Motherwell WB, Roberts LR. J. Chem. Soc., Chem. Commun. 1992; 1582
- 6a Dolbier JrW. R, Burkholder CR. J. Org. Chem. 1990; 55: 589
- 6b Ilchenko NO, Hedberg M, Szabó KJ. Chem. Sci. 2017; 8: 1056
- 6c Werth J, Uyeda C. Chem. Sci. 2018; 9: 1604
- 7a Muthusamy S, Gunanathan C. Synlett 2003; 1599
- 7b Hilt G, Galbiati F. Synthesis 2006; 3589
- 7c Lindsay VN. G, Lin W, Charette AB. J. Am. Chem. Soc. 2009; 131: 16383
- 7d Lindsay VN. G, Nicolas C, Charette AB. J. Am. Chem. Soc. 2011; 133: 8972
- 7e Negretti S, Cohen CM, Chang JJ, Guptill GM, Davies HM. L. Tetrahedron 2015; 71: 7415
- 7f Lehner V, Davies HM. L, Reiser O. Org. Lett. 2017; 19: 4722
- 7g Sun G.-J, Gong J, Kang Q. J. Org. Chem. 2017; 82: 796
- 7h Tindall DJ, Werlé C, Goddard R, Philipps P, Farès C, Fürstner A. J. Am. Chem. Soc. 2018; 140: 1884
- 7i Lindsay VN. G. Rhodium(II)-Catalyzed Cyclopropanation. In Rhodium Catalysis in Organic Synthesis: Methods and Reactions. Tanaka K. Wiley-VCH; Weinheim: 2018: 433
- 8a Doyle MP, Hu W, Phillips IM, Moody CJ, Pepper AG, Slawin AG. Z. Adv. Synth. Catal. 2001; 343: 112
- 8b Doyle MP, Hu W. Adv. Synth. Catal. 2001; 343: 299
- 8c Gharpure SJ, Shukla MK, Vijayasree U. Org. Lett. 2010; 11: 5466
- 8d Vanier SF, Larouche G, Wurz RP, Charette AB. Org. Lett. 2009; 12: 672
- 8e Nani RR, Reisman SE. J. Am. Chem. Soc. 2013; 135: 7304
- 8f Gu H, Huang S, Lin X. Org. Biomol. Chem. 2019; 17: 1154
- 9a Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem. Rev. 2010; 110: 704
- 9b Colby DA, Tsai AS, Bergman RG, Ellman JA. Acc. Chem. Res. 2012; 45: 814
- 9c Piou T, Rovis T. Acc. Chem. Res. 2018; 51: 170
- 10 Piou T, Rovis T. J. Am. Chem. Soc. 2014; 136: 11292
- 11 Piou T, Romanov-Michailidis F, Ashley MA, Romanova-Michaelides M, Rovis T. J. Am. Chem. Soc. 2018; 140: 9587
- 12a Piou T, Rovis T. Nature 2015; 527: 86
- 12b Zhang Y, Liu H, Tang L, Tang H.-J, Wang L, Zhu C, Feng C. J. Am. Chem. Soc. 2018; 140: 10695
- 13 Duchemin C, Cramer N. Chem. Sci. 2019; 10: 2773
- 14 Phipps EJ. T, Rovis T. J. Am. Chem. Soc. 2019; 141: 6807
- 15 General Procedure N-Enoxyphthalimide (0.1 mmol), catalyst [Cp*CF3RhCl2]2 (5 mol%, 0.005 mmol, 3.7 mg), and CsOAc (2 equiv, 0.2 mmol, 38.5 mg) were weighed in a 1-dram vial with a magnetic stir bar. TFE (0.2 M, 500 μL) was added followed by alkene (1.2 equiv, 0.12 mmol). The vial was sealed with a screw cap and stirred at room temperature for 12 h. Upon completion judged by TLC, the crude solution was diluted with EtOAc and partitioned with the addition of DI water. The aqueous layer was extracted three times with EtOAc, and the combined organic extracts were filtered through a pad of Celite® and Na2SO4 then concentrated. The crude residue was purified by flash chromatography (hexane/EtOAc, 19:1) to afford the cyclopropane product.Compound 3ad: Purified by flash chromatography eluting with 5% EtOAc in hexanes; 21.0 mg, 98% yield, colorless oil, R f = 0.73 (4:1 hexanes/EtOAc). 1H NMR (500 MHz, CDCl3): δ = 8.06–7.97 (m, 2 H), 7.59–7.51 (m, 1 H), 7.51–7.43 (m, 2 H), 2.51 (dd, J = 7.3, 5.4 Hz, 1 H), 1.70–1.39 (m, 10 H), 1.19 (dt, J = 12.6, 6.1 Hz, 1 H), 0.95 (dd, J = 7.4, 4.0 Hz, 1 H). 13C NMR (126 MHz, CDCl3): δ = 198.4, 139.1, 132.5, 128.6, 128.2, 38.0, 35.6, 32.2, 28.48, 26.3, 26.2, 26.0, 21.5. IR (neat): 2921, 2850, 1664, 1447, 1396, 1216, 980, 718, 689 cm–1. LRMS (ESI APCI): m/z calcd for C15H18O [M + H]: 215.1; found: 215.1.
- 16a Corey EJ, Chaykovsky M. J. Am. Chem. Soc. 1965; 87: 1353
- 16b Carlson RG, Behn NS. J. Org. Chem. 1967; 32: 1363
- 16c Bellucci G, Chiappe C, Lo Moro G, Ingrosso G. J. Org. Chem. 1995; 60: 6214
For a recent selection of many diazo decomposition reactions, see:
For a recent selection of Simmons–Smith-type reactions, see:
Regarding exo-methylene alkenes:
For selected recent examples of Rh-catalyzed cyclopropanations, see:
Diastereoselectivity assigned by analogy to other three-membered rings formed from 4-substituted-exocyclic alkenes: