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Synlett 2009(1): 129-132  
DOI: 10.1055/s-0028-1087377
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© Georg Thieme Verlag Stuttgart ˙ New York

Silver-Catalyzed C-H Insertion Reactions with Donor-Acceptor Diazoacetates

Carl J. Lovely*, Jaime A. Flores, Xiaofeng Meng, H. V. Rasika Dias*
Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019, USA
Fax: +1(817)2723808; e-Mail: lovely@uta.edu; e-Mail: dias@uta.edu;
Further Information

Publication History

Received 5 September 2009
Publication Date:
12 December 2008 (online)

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Abstract

In this paper we describe the first examples of carbene transfer with donor-acceptor diazoacetates and the silver tris(pyrazolyl)borate complex {HB[3,5-(CF3)2Pz]3}Ag(THF). These reactions generally proceed in good yields and exhibit improved selectivities compared to simple diazoacetates.

Key words

organometallic - tris(pyrazolyl)borate - silver - atom transfer - chemoselective

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General Procedure for Catalysis by Carbene-Transfer Reactions with Catalyst {HB[3,5-(CF 3 ) 2 Pz] 3 }Ag(THF): Methyl phenyldiazoacetate or methyl styryldiazoacetate (0.25 mmol) dissolved in the substrate (5 mL) was added by syringe pump over a period of ca. 3 h to a stirred solution of the catalyst (0.005 g, 0.01 mmol) in the substrate (10 mL) in a foil-shielded, round-bottomed flask. The resulting mixture was stirred for 6 h at r.t., concentrated and the residue was purified by flash chromatography on silica gel (2% Et2O-PE for hydrocarbons, 5-20% Et2O-PE for ethers) to yield oily transparent or white solid products. The isolated yields are based on the average of at least two experiments and on the amount of diazoacetate used.

20

Methyl 2-Phenyl-3-methylhexanoate: yield: 40.2 mg (73%); diastereoisomer ratio = 1.2:1. ¹H NMR (300 MHz, CDCl3): δ = 7.19-7.36 (m, 10 H, ArH), 3.624 (s, 3 H, OMe), 3.620 (s, 3 H, OMe), 3.24 (d, J = 10.7 Hz, 1 H, CHPh), 3.23 (d, J = 10.3 Hz, 1 H, CHPh), 2.11-2.28 (m, 2 H, CH), 1.01-1.50 (m, 8 H, CH2), 0.98 (d, J = 6.5 Hz, 3 H, Me), 0.89 (t, J = 6.9 Hz, 3 H, Me), 0.73 (t, J = 6.9 Hz, 3 H, Me), 0.65 (d, J = 6.9 Hz, 3 H, Me). ¹³C NMR (125 MHz, CDCl3): δ = 174.54, 174.49, 138.19, 138.14, 128.61, 128.58, 128.42, 128.39, 127.14, 58.8, 55.5, 51.7, 37.6, 36.2, 36.1, 35.6, 19.9, 19.4, 17.8, 16.6, 14.2, 14.0. IR (neat): 3087, 3064, 3029, 2959, 2932, 2873, 1738 cm-¹. HRMS (ESI): m/z [M + H]+ calcd for C14H21O2: 221.1536; found: 221.1537.