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Synlett 2014; 25(3): 417-422
DOI: 10.1055/s-0033-1340290
DOI: 10.1055/s-0033-1340290
letter
(EtO)3SiH-Promoted Palladium-Catalyzed Isomerization of Olefins: Convenient Synthesis of Internal Alkenes from Terminal Alkenes
Further Information
Publication History
Received: 16 September 2013
Accepted after revision: 17 October 2013
Publication Date:
04 December 2013 (online)
![](https://www.thieme-connect.de/media/synlett/201403/lookinside/thumbnails/10.1055-s-0033-1340290-1.jpg)
Abstract
The catalytic activity of an in situ forming palladium catalyst system generated from PdCl2(PPh3)2 and hydrosilane [(EtO)3SiH] was revealed in the one-carbon migration and isomerization of 4,4-biaryl-substituted 1-butenes, in which the (EtO)3SiH plays a key role in the palladium-catalyzed one-carbon migration and subsequent isomerization of terminal alkenes. This catalytic protocol is applied in the synthesis of a key building block of cassumunin C in high yield and promising selectivity.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
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- 20 Typical Procedure for the Palladium-Catalyzed Isomerization 4,4-Diarylbut-1-enes (0.5 mmol), (EtO)3SiH (0.1 mmol, 18.5 μL, 0.2 equiv) and a catalytic amount of Pd(Ph3P)2Cl2 (0.005 mmol, 1 mol%) were added to a dry tube, and then the mixture was solved with dry THF (1 mL). The resulting mixture was stirred at 60 °C for 10 h. The mixture was then cooled to r.t., quenched by the addition of H2O, and extracted by the addition of CH2Cl2. The organic layer was washed with H2O, dried over Na2SO4, and concentrated. The residue was purified by flash column chromatography to give corresponding 4,4-diarylbut-1-enes. All the products were confirmed by GC–MS, NMR and IR spectrosopy. These data are provided in the Supporting Information. Analytical Data for 1-Methyl-2-(1-phenylbut-2-enyl)benzene (3a) 1H NMR (400 MHz, CDCl3): δ = 7.32 (t, J = 6.8 Hz, 2 H), 7.23 (J = 6.8 Hz, 3 H), 7.14 (d, J = 6.8 Hz, 2 H), 6.87 (d, J = 6.8 Hz, 2 H), 5.94 (dd, J = 13.6, 7.6 Hz, 1 H), 5.74–5.68 (m, 0.14 H), 5.47 (dq, J = 14.8, 6.4 Hz, 0.88 H), 5.02 (d, J = 9.6 Hz, 0.14 H), 4.66 (d, J = 7.2 Hz, 0.86 H), 3.81 (s, 3 H), 1.77 (d, J = 6.4 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.0, 144.6, 136.5, 133.9, 129.5, 128.5, 128.3, 126.7, 126.1, 113.8, 55.3, 53.3, 18.0 ppm. GC–MS: m/z calcd for C17H18 [M]+: 222.3; found: 222.1. IR (KBr): νmax = 3412, 3059, 3025, 3000, 2957, 2931, 2853, 2835, 1653, 1608, 1510, 1493, 1448, 1302, 1250, 1178, 1150, 1034, 971, 830, 700, 560 cm–1.
Selected reviews:
Selected examples:
For recent examples, see:
Metal hydrides generated using hydrosilanes have been reported previously, for selected examples see: