102003-93-0Relevant academic research and scientific papers
High-Throughput Screening of Reductive Amination Reactions Using Desorption Electrospray Ionization Mass Spectrometry
Cooks, R. Graham,Ferreira, Christina R.,Li, Yangjie,Logsdon, David L.,Paschoal Sobreira, Tiago Jose,Thompson, David H.
supporting information, p. 1647 - 1657 (2020/10/26)
This study describes the latest generation of a high-throughput screening system that is capable of screening thousands of organic reactions in a single day. This system combines a liquid handling robot with desorption electrospray ionization (DESI) mass spectrometry (MS) for a rapid reaction mixture preparation, accelerated synthesis, and automated MS analysis. A total of 3840 unique reductive amination reactions were screened to demonstrate the throughputs that are capable with the system. Products, byproducts, and intermediates were all monitored in full-scan mass spectra, generating a complete view of the reaction progress. Tandem mass spectrometry experiments were conducted to verify the identity of the products formed. The amine and electrophile reactivity trends represented in the data match what is expected from theory, indicating that the system accurately models the reaction performance. The DESI results correlated well with those generated using more traditional mass spectrometry techniques like liquid chromatography-mass spectrometry, validating the data generated by the system.
Catalytic C - H amination with unactivated amines through copper(II) amides
Wiese, Stefan,Badiei, Yosra M.,Gephart, Raymond T.,Mossin, Susanne,Varonka, Matthew S.,Melzer, Marie M.,Meyer, Karsten,Cundari, Thomas R.,Warren, Timothy H.
supporting information; experimental part, p. 8850 - 8855 (2011/02/24)
En route to catalysis: Two equivalents of the three-coordinate copper(II) amide [(Cl2NN)Cu]-NHAd participate in stoichiometric C - H amination by a H-atom abstraction/radical capture sequence. This active species may be generated through a copper(II) tert-butoxide intermediate to allow for the unprecedented catalytic amination of sp3-C - H bonds with unactivated alkylamines. This method greatly expands the range of amines for catalytic C - H amination since most protocols require N-based electron-withdrawing groups.
Free-Radical Chemistry of Imines
Tomaszewski, Miroslaw J.,Warkentin, John,Werstiuk, Nick H.
, p. 291 - 322 (2007/10/02)
Aryl radicals bearing an aldimino functional group as part of an ortho substituent cyclized by addition to C and/or N of the imino group.When the choice was between 5-exo closure to C and 6-endo closure to N, the former predominated.However, 6-endo closure to C predominated over 5-exo cyclization to N in isomeric imines.Absolute values of cyclization rate constants were determined and an explanation for the unusual 6-endo preference is offered.Chiral induction in 6-endo cyclization to C of an aldimine from D-glyceraldehyde acetonide was observed, and its sense was determined.
Chiral Induction in Aryl Radical Cyclization to the Aldimino Functional Group
Tomaszewski, Miroslaw J.,Warkentin, John
, p. 966 - 968 (2007/10/02)
6-endo Cyclization of aryl radicals to carbon of aldimino double bonds (N-5/C-6) in chiral ortho-substituents afforded 1,2,3,4-tetrahydroisoquinolines in yields to 69percent, with 58percent d.e. and 97percent e.e., while 5-exo cyclization to carbon in isomeric radicals (C-5/N-6 aldimine), leading to indanamines, was highly regioselective and fast, k5-exo = 3.9 * 108 s-1 at 80 deg C.
