Application of dialkyl azodicarboxylate frameworks featuring multi-functional properties

Abstract

The application of dialkyl azodicarboxylates as versatile reagents in Mitsunobu, oxidation, electrophilic, amination and carbonylation reactions is reviewed.

Asymmetric Organocatalysis with Chiral Covalent Organic Frameworks

“…51 While many classical transformations have been established, direct addition to azodicarboxylates is one of the most useful protocols. 52 To this end, Wang et al applied their bifunctional chiral COFs into the amination of ethyl 2oxocyclopentane-1-carboxylate 17 with di-tert-butyl diazene-1,2-dicarboxylate 18. It turned out that the cyclohexane-1,2-diamine-based TAH-CCOF2 21 afforded the product 19 in identical chirality as to the molecular motif 20, indicating that they should undergo the same transition state.…”

“…While many classical transformations have been established, direct addition to azodicarboxylates is one of the most useful protocols52 . To this end, Wang et al applied their bifunctional chiral COFs into the amination of ethyl 2-oxocyclopentane-1carboxylate 17 with di-tert-butyl diazene-1,2-dicarboxylate 18.…”

Progress of Dialkyl Azodicarboxylates in Organic Transformations

“…[8] They are also utilized for conversion of carbonyl compounds into optically active compounds. [9] The carbonylation reaction using azodicarboxylates is well documented [6,10,11] and their use as substrate in construction of CÀ N bond has also been achieved. [12][13][14] However, in recent past, the oxidative abilities of these azo compounds have been investigated in other organic transformations.…”

“…[9] The carbonylation reaction using azodicarboxylates is well documented [6,10,11] and their use as substrate in construction of CÀ N bond has also been achieved. [12][13][14] However, in recent past, the oxidative abilities of these azo compounds have been investigated in other organic transformations. Oxidative coupling or cross dehydrogenative coupling (CDC) [15][16][17] and oxidative Ugi-type reaction sequence [18] require oxidant, and dialkyl azodicarboxylates are suitable candidates for these oxidation reactions.…”

Synthesis of N‐Aryl‐ and N‐Alkenylhydrazides through C(sp2)−N Bond Construction

“…On the other hand, azo compounds with electron‐withdrawing groups are also used as hydrazino sources owing to the electrophilic property of their N=N bonds, which can be attacked by aryl‐/alkenyl‐ anions or radicals to generate target hydrazides (Figure 4). These compounds cover the well‐known azodicarboxylic esters and derivatives 38–43 [1b,15] . Azo compounds with one electron‐withdrawing group are also used in electrophilic hydrazidation, with tert ‐butyl aryl azocarboxylates 44 , arylazo ketones 45 , and even arylazo sulfones 46 as examples.…”