Hydrogen‐Borrowing and Interrupted‐Hydrogen‐Borrowing Reactions of Ketones and Methanol Catalyzed by Iridium

作者: Di Shen , Darren L. Poole , Camilla C. Shotton , Anne F. Kornahrens , Mark P. Healy

DOI: 10.1002/ANIE.201410391

关键词:

摘要: Reported herein is the use of catalytic [{Ir(cod)Cl}2] to facilitate hydrogen-borrowing reactions ketone enolates with methanol at 65 °C. An oxygen atmosphere accelerates process, and when combined a bulky monodentate phosphine ligand, interrupts cycle by preventing enone reduction. Subsequent addition pro-nucleophiles reaction mixture allowed one-pot methylenation/conjugate protocol be developed, which greatly expands range products that can made this methodology.

参考文章(33)
C. Gunanathan, D. Milstein, Applications of acceptorless dehydrogenation and related transformations in chemical synthesis. Science. ,vol. 341, pp. 1229712- 1229712 ,(2013) , 10.1126/SCIENCE.1229712
Phillip. J. Black, Gerta Cami-Kobeci, Michael G. Edwards, Paul A. Slatford, Michael K. Whittlesey, Jonathan M. J. Williams, Borrowing hydrogen: iridium-catalysed reactions for the formation of C–C bonds from alcohols Organic and Biomolecular Chemistry. ,vol. 4, pp. 116- 125 ,(2006) , 10.1039/B511053J
Shinji Ogawa, Yasushi Obora, Iridium-catalyzed selective α-methylation of ketones with methanol Chemical Communications. ,vol. 50, pp. 2491- 2493 ,(2014) , 10.1039/C3CC49626K
Bi Jiang, Yuee Feng, Elon A. Ison, Mechanistic investigations of the iridium(III)-catalyzed aerobic oxidation of primary and secondary alcohols. Journal of the American Chemical Society. ,vol. 130, pp. 14462- 14464 ,(2008) , 10.1021/JA8049595
Michael I. Hall, Simon J. Pridmore, Jonathan M. J. Williams, Alkenes from Alcohols by Tandem Hydrogen Transfer and Condensation Advanced Synthesis & Catalysis. ,vol. 350, pp. 1975- 1978 ,(2008) , 10.1002/ADSC.200800338
Michael Renz, Bernard Meunier, 100 Years of Baeyer–Villiger Oxidations European Journal of Organic Chemistry. ,vol. 1999, pp. 737- 750 ,(1999) , 10.1002/(SICI)1099-0690(199904)1999:4<737::AID-EJOC737>3.0.CO;2-B
Ken Motokura, Noriaki Fujita, Kohsuke Mori, Tomoo Mizugaki, Kohki Ebitani, Koichiro Jitsukawa, Kiyotomi Kaneda, None, Environmentally Friendly One‐Pot Synthesis of α‐Alkylated Nitriles Using Hydrotalcite‐Supported Metal Species as Multifunctional Solid Catalysts Chemistry: A European Journal. ,vol. 12, pp. 8228- 8239 ,(2006) , 10.1002/CHEM.200600317
Andrew J. A. Watson, Aoife C. Maxwell, Jonathan M. J. Williams, Ruthenium-catalysed oxidative synthesis of heterocycles from alcohols Organic and Biomolecular Chemistry. ,vol. 10, pp. 240- 243 ,(2012) , 10.1039/C1OB06516E
Yang Li, Haoquan Li, Henrik Junge, Matthias Beller, Selective ruthenium-catalyzed methylation of 2-arylethanols using methanol as C1 feedstock. Chemical Communications. ,vol. 50, pp. 14991- 14994 ,(2014) , 10.1039/C4CC06933A