Aryne Relay Chemistry en Route to Aminoarenes: Synthesis of 3-Aminoaryne Precursors via Regioselective Silylamination of 3-(Triflyloxy)arynes

Abstract

A facile synthetic method for preparing 3-amino-2-silylaryl triflates via regioselective silylamination of 3-(triflyloxy)arynes with N-silylamines is described. Fluoride-mediated generation of 3-aminobenzyne from 3-amino-2-silylphenyl triflate, easily prepared by this method, in the presence of various arynophiles efficiently afforded diverse aniline derivatives, including a 5-aminocoumarin derivative, demonstrating the utility of aryne relay approach.

Substantial Intramolecular Charge Transfer Induces Long Emission Wavelengths and Mega Stokes Shifts in 6-Aminocoumarins

“…The TICT explanation has subsequently been accepted and referenced by many research groups. [19][20][21][22][23] In recent years, 6-aminocoumarins have turned out to be a useful platform for developing various fluorescent sensors. 19,[24][25][26][27][28] Along with this rapid development, several research groups started to argue that no direct experimental evidence supports the TICT model in 6aminocoumarins, using both fluorescence lifetime and pressure-dependent fluorescence intensity measurements as their justification.…”

Modular Synthesis of Unsymmetrical Doubly-ring-fused Benzene Derivatives Based on a Sequential Ring Construction Strategy Using Oxadiazinones as a Platform Molecule

“…Furthermore, tetrahydroanthracene 16d bearing a morpholino group was successfully synthesized by the reaction of 13a with 3-morpholinobenzyne generated from the corresponding o-silylaryl triflate-type precursor, 19 which was prepared from 2-iodo-1,3-bis(triflyloxy)benzene via 3-(triflyloxy)benzyne. 20 Another type of aryne precursor 21 was also applicable to this transformation.…”

“…Oxidative aromatization of tetrahydroanthracene 16c using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) 22 efficiently afforded 2,3-dimethoxy-9,10-diphenylanthracene (19) in good yield (Scheme 3). This result indicates that the sequential ring construction approach also renders unsymmetrical multi-substituted anthracenes easily available, further expanding the synthetic utility of the method.…”

Discussion Addendum for: The Direct Acyl-Alkylation of Arynes. Preparation of Methyl 2-(2-acetylphenyl)acetate

“…57,58,59 In 2016, Yoshida reported an advancement of this concept. 60 The Li group discovered that these latent 1,2benzdiynes can also participate in ene reactions. 61…”