119th General Meeting of the KCS

Type Symposium
Area [SRC 심포지엄] New Trends and Developments in Organic Synthesis
Room No. 303호
Time WED 14:50-:
Code KCS5-3
Subject Transition Metal Catalyzed Synthesis of Amides and Amines Through Alcohol Activation
Authors 이정빈, 홍순혁*
서울대학교 화학부, Korea
Abstract Atom-economical amide synthesis is one of the top challenges in synthetic organic chemistry. The amide bond is the key backbone of all natural peptides in biological systems and is also an important functional group in all branches of organic chemistry. Traditionally, amides have been synthesized by reactions of carboxylic acids and their derivatives with amines, which suffers from harsh conditions and a large amount of byproducts. Over the past few years, chemists have extensively addressed new methodologies for the formation of amide bonds, aiming more efficient and environmentally benign pathway. During our studies on the atom-economical and environmentally benign amidation from alcohol with amine catalyzed by ruthenium-based organometallic complexes, we developed new amide and secondary amine bond synthetic methods from different N- or alcohol source. Amides were formed directly from azides in place of amines and we also developed a method which converts esters to amides and secondary amines in one-pot. In ester activation method, amide was formed by ester-amide exchange which generates alcohol in situ which is subsequently transformed to secondary amine via hydrogen autotransfer. These synthetic protocols with high atom economy generates hydrogen or water as the non-harmful by-products, expanding the synthetic versatility and efficiency of amide and amine bond formation. 1 Z. Fu, J. Lee, S. H. Hong, Org. Lett., 2012, 14, 6028-6031. 2 J. Lee, S. Muthaiah, S. H. Hong, Adv. Synth. Catal. 2014, 356, 2653-2660. 3 R. Larock, Comprehensive Organic Transformations, Wiley-VCH, New York 1999. 4 a) T. Ohshima, Y. Hayashi, K. Agura, Y. Fujii, A. Yoshiyama, K. Mashima, Chem. Commun. 2012, 48, 5434; b) B. Gnanaprakasam, D. Milstein, J. Am. Chem. Soc. 2011, 133, 1682-1685.
E-mail lomanya@snu.ac.kr