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Synlett 2012; 23(19): 2749-2752
DOI: 10.1055/s-0032-1316555
DOI: 10.1055/s-0032-1316555
cluster
Palladium-Catalyzed Oxidative Arylalkylation of Unactivated Alkenes: Dual C–H Bond Cleavage of Anilines and Acetonitrile
Further Information
Publication History
Received: 26 April 2012
Accepted after revision: 26 May 2012
Publication Date:
16 July 2012 (online)
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Abstract
A palladium-catalyzed oxidative arylalkylation of unactivated alkenes involving dual C–H bond cleavage of arene and acetonitrile was developed. This reaction was promoted by pyridine as a ligand, and the ratio of palladium to pyridine is vital for this transformation. A series of nitrile-containing indolines were efficiently provided in moderate to good yields.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
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References and Notes
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- 14 General Procedure for Pd-Catalyzed Oxidative Arylalkylarion of 1 In a sealed dry glass tube, alkene 1a (37.8 mg, 0.02 mmol), Pd(OAc)2 (4.6 mg, 0.02 mmol), AgF (126.8 mg, 1.0 mmol), PhI(OCOt-Bu)2 (203.1 mg, 0.5 mmol), and pyridine (1.3 μL, 0.016 mmol) were dissolved in dry MeCN (2.0 mL). The mixture was stirred at 100 °C for 24 h. Then the solvent was removed under vacuum, and the residue was purified by column chromatography on silica gel to give the product 2a. 1H NMR (400 MHz, CDCl3): δ = 8.21 (d, J = 8.4 Hz, 1 H), 7.28–7.24 (m, 1 H), 7.09 (d, J = 4.0 Hz, 2 H), 3.98 (d, J = 10.8 Hz, 1 H), 3.78 (d, J = 10.4 Hz, 1 H), 2.24 (s, 3 H), 2.19–2.14 (m, 2 H), 2.04–1.99 (m, 2 H), 1.44 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 168.6, 142.2, 135.8, 128.6, 124.0, 122.0, 119.4, 117.0, 60.4, 43.0, 36.9, 26.4, 24.2, 12.8. HRMS (EI): m/z calcd [M+]: 228.1263; found: 228.1266
For recent reviews on the oxidative difunxtionalization of alkenes, see:
For conjugated dienes, see:
The Pd-catalyzed oxidative enynes cyclization is the only one case involving intramolecular dicabonation of alkenes, see:
For similar transformations, see: