Automated Serendipity with Self‐Optimizing Continuous‐Flow Reactors. Issue 28 (25th August 2015)

• Record Type: Journal Article
• Authors: Amara, Zacharias; Streng, Emilia S.; Skilton, Ryan A.; Jin, Jing; George, Michael W.; Poliakoff, Martyn
• Is Part Of: European journal of organic chemistry. Issue 28(2015)
• Page Start: 6141
• Page End: 6145
• Publication Date: 2015-08-25
• Subjects: Self‐optimization -- Flow chemistry -- Aniline -- Alkylation -- Acid‐base ­catalysis -- Supercritical fluids; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201500980
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: A self‐optimizing approach is used as a tool for targeting known and unknown materials in the continuous reaction of aniline, dimethyl carbonate (DMC) and tetrahydrofuran (THF) in supercritical CO2 on γ‐Al2 O3 . The study led to the formation of methylated anilines or carbamate derivatives and unusual addition products with THF including pyrrolidines and N ‐alkylated anilines. The identification of these products leads to the development of a plausible mechanism for the reactions. The system not only demonstrates a high flexibility that the self‐optimization approach provides, including the ability to optimize for a variety of products by using a single catalyst, but also the ability to discover unexpected and original synthetic reactions. Abstract : Self‐optimizing continuous‐flow reactors have been used to investigate the reaction of aniline with THF and DMC. High‐selectivity profiles were obtained for the synthesis of methylated anilines or N ‐phenylpyrrolidines. By combining the three components in a single reaction system, a tandem alkylation reactivity leading to diversely alkylated anilines was discovered.