Superbase‐Promoted Addition of Acetylene Gas to the C=N Bond

Abstract

A new Csp3–Csp bond forming reaction is reported: the C=N bond of widespread imines reacts with acetylene gas in the presence of superbase KOtBu/DMSO at room temperature to afford terminal α‐aminoacetylenes in up to 94 % yield. The reaction allows nitrogen heterocycles, e.g. 3H‐indoles, to be directly cross‐coupled with acetylene gas.

Perylene-based non-covalent functionalization of 2D materials

“…By additional functionalization with primary amines, the generic parent perylene diimide (PDI) chromophore can be obtained. [11] Moreover, the chemical modification can also take place in the equatorial region, both at the ortho [12] and bay [13] positions. Since the early 1990s the interaction of perylene-based derivatives has been studied on graphite by means of scanning tunneling microscopy (STM).…”

Two classes of heterocycles—6,8‐dioxabicyclo[3.2.1]octanes and cyclopentenols from the same reagents: A quantum‐chemical comparison of mechanism

“…The common key intermediates in the assembling of dioxabicyclo[3.2.1]octanes and cyclopentenols are 1,5‐diketones 1 which are formed via nucleophilic addition of a ketone to acetylene followed by the addition of second molecule of a ketone to the activated double bond of adduct (Scheme ).…”

“…Protonation of the latter and a 1,3‐prototropic rearrangement give acylcyclopentenol 7 (Scheme ) . Thus, the competitive reactions result in formation of either acylcyclopentenols or dioxabicyclooctanes …”

Understanding the solubilization of Ca acetylide with a new computational model for ionic pairs

“…39 Other organometallic acetylides as that of Au, 40 Bi, 39 Pt 41 also undergo dipolar cycloaddition to azides; the corresponding AAC reaction products are potent precursors to a wide range of substituted heterocyclic compounds. 39 Activation of HC≡CH or RC≡CH via acetylide formation is necessary in CuAAC [42][43][44][45] and other 46 reactions. It was proposed that "any s-acetylide that can effectively recruit a p-bound copper atom will undergo annulation with a compatible dipolar partner."…”

“…52 Acetylene chemistry in dimethyl sulfoxide (DMSO) under basic and super-basic conditions is a valuable and indispensable tool of modern organic chemistry. 46,[53][54][55][56] Greater potential of practically valuable synthesis with CaC 2 can be realized through understanding the unique performance of DMSO solutions.…”