Synthesis of medicinally relevant oxalylamines via copper/Lewis acid synergistic catalysis

Abstract

Allylamines have long been recognized as valuable synthons because of their excellent reactivity in organic synthesis. Here, an efficient amination reaction of allenyl ethers via copper/Lewis acid synergistic catalysis has been established, providing straightforward access to diverse functionalized Z-oxalylamines and E-halogenated oxalylamines in good to excellent yields with high regio- and stereoselectivities. The developed method tolerates more than 100 examples that include late-stage functionalization of bioactive molecules, and features gram-scale synthesis of oxalylamines with high turnover number (TON > 1000) under mild and simple conditions. The applicability of the protocol is further demonstrated with the construction of drug molecules.

The cobalt(ii)-catalyzed acyloxylation of picolinamides with bifunctional silver carboxylateviaC–H bond activation

“…TEMPO had no inhibitory effects on the reactions, which indicated that no radical process was involved in the acyloxylation reaction (Scheme 3b). 18 In order to confirm the lack of any radical mechanism, butylated hydroxytoluene (BHT) was also employed. As the amount of BHT included was increased, the inhibition of acyloxylation became obvious.…”

Palladium‐Catalyzed anti‐Markovnikov Halosulfonamidation of Unactivated Alkene†

“…However, the anti ‐Markovnikov aminopalladation to yield linear amines has been hitherto underexploited in comparison with the abundant studies on the Markovnikov amination. [ 29‐32 ] Towards the construction of linear amine, some viable established methods are: conjugate alkene strategy, [ 33‐38 ] directing group strategy, [ 39‐41 ] and π‐allyl metal strategy, [ 42‐43 ] where selectivity is governed by substrate directivity. In addition to these activation tactics, there are only a limited number of examples focusing on anti ‐Markovnikov amination of unactivated olefins (Scheme 1A).…”

“…The issues to be solved are: i) overcoming the intrinsic effects of regioselective aminopalladation sequence, especially in the absence of adscititious halide; ii) guiding the subsequent halogenation selectively over undesired β ‐H elimination by employing an appropriate oxidant, and iii) simultaneously yielding linear amine with a reactive halogen handle. Based on the oxidative amination [ 45‐46 ] and our research on nucleophilic amination reactions, [ 36‐38 ] we envisioned that a halogenting agent serves as a halogen sourse [ 47‐48 ] to saturate the coordination sites for the anti ‐Markovnikov aminopalladation process. On the other hand, it promotes reductive elimination to provide the corresponding alkyl C—X bond with the high‐valent palladium pathway.…”

Influence of anions on the synthesis of Cu(i)-based coordination polymers along with a series of derived materials for selective photocatalytic properties

“…Interesting physical properties and structural diversity make the design and synthesis of novel organic-inorganic hybrid materials an active field in coordination chemistry. [1][2][3][4] In this field, Cu-based compounds have been of increasing interest for their intriguing topologies, 5,6 which can be widely used in photocatalysis. 7,8 Univalent Cu ion possesses the coordination numbers 2-4, and bivalent Cu ion coordination configuration ranges from four-connected planar mode to five-connected pyramid and six-connected octahedron, etc., which make it difficult to predict the structure of the products.…”