602261-94-9Relevant academic research and scientific papers
Isocyanide 2.0
Ahmadian-Moghaddam, Maryam,D?mling, Alexander,Patil, Pravin
supporting information, p. 6902 - 6911 (2020/11/09)
The isocyanide functionality due to its dichotomy between carbenoid and triple bond characters, with a nucleophilic and electrophilic terminal carbon, exhibits unusual reactivity in organic chemistry exemplified for example in the Ugi reaction. Unfortunately, the over proportional use of only a few isocyanides hampers novel discoveries about the fascinating reactivity of this functional group. The synthesis of a broad range of isocyanides with multiple functional groups is lengthy, inefficient, and exposes the chemist to hazardous fumes. Here we present an innovative isocyanide synthesis overcoming these problems by avoiding the aqueous workup which we exemplify by parallel synthesis from a 0.2 mmol scale performed in 96-well microtiter plates up to a 0.5 mol multigram scale. The advantages of our methodology include an increased synthesis speed, very mild conditions giving access to hitherto unknown or highly reactive classes of isocyanides, rapid access to large numbers of functionalized isocyanides, increased yields, high purity, proven scalability over 5 orders of magnitude, increased safety and less reaction waste resulting in a highly reduced environmental footprint. For example, the hitherto believed to be unstable 2-isocyanopyrimidine, 2-acylphenylisocyanides and even o-isocyanobenzaldehyde could be accessed on a preparative scale and their chemistry was explored. Our new isocyanide synthesis will enable easy access to uncharted isocyanide space and will result in many discoveries about the unusual reactivity of this functional group. This journal is
Efficient isocyanide-less isocyanide-based multicomponent reactions
Neochoritis, Constantinos G.,Stotani, Silvia,Mishra, Bhupendra,D?mling, Alexander
supporting information, p. 2002 - 2005 (2015/04/27)
Isocyanides are the Jekyll and Hyde of organic chemistry allowing for extremely interesting transformations that are not only extremely odorous but also noxious. Therefore, an isocyanide-less isocyanide-based multicomponent reaction (IMCR) has been developed, and this protocol is expected to replace many of the old procedures in the future not only in IMCR but in other areas of organic chemistry as well.
A cation-directed two-component cascade approach to enantioenriched pyrroloindolines
Wolstenhulme, Jamie R.,Cavell, Alex,Grediak, Matija,Driver, Russell W.,Smith, Martin D.
, p. 13585 - 13588 (2015/02/19)
A cascade approach to complex pyrroloindolines bearing all-carbon quaternary stereocentres has been developed. This two-component process uses a chiral ammonium salt to control diastereo- and enantioselectivity in the addition of isocyanides to functionalized alkenes to afford pyrroloindolines with up to three stereocentres. A mechanistic proposal involving intramolecular hydrogen bond activation of the isocyanide is described.
Ugi reactions with ammonia offer rapid access to a wide range of 5-aminothiazole and oxazole derivatives
Thompson, Mark J.,Chen, Beining
experimental part, p. 7084 - 7093 (2010/01/06)
(Chemical Equation Presented) A series of Ugi reactions has been successfully performed using ammonia as the amine component, employing 2,2,2-trifluoroethanol as a non-nucleophilic solvent in order to suppress known side reactions. Utilizing concentrated aqueous ammonia as a convenient source, this approach offered a simple, one-step assembly of Ugi adducts suitable for elaboration into a variety of 5-aminoazole compounds through postcondensation modifications. Free or N-substituted 5-aminothiazoles and 5-(trifluoroacetamido) oxazoles were all prepared by this improved methodology. The scope of the synthetic route developed and application of the different products are discussed.
