Three-Component Aminoselenation of Arynes

Abstract

The three-component coupling of tertiary amines, arynes, and aryl selenium bromide or diaryl diselenide as an electrophilic selenium source allowing the synthesis of 2selanyl aniline derivatives is reported. This aminoselenation reaction of arynes installs a C−N and C−Se bond under mild conditions, and the products are formed in moderate to good yields. This reaction is compatible with various functional groups, and the preliminary studies on the mechanism of the reaction is also provided.

Metal‐Free Synthesis of Selenodihydronaphthalenes by Selenoxide‐Mediated Electrophilic Cyclization of Alkynes

“…[13] For instance, the diaryl selenide A is used as an antitumor agent, [14] the carboxylic acid B is a retinoic acid receptor (RAR) agonist, [15] and the nitro compound C can serve as a thioredoxin reductase (TR) and glutathione reductase (GR) inhibitor (Scheme 1a). [16] With these unique features, the incorporation of selenium groups into arenes [17] and alkenes [18] has gained much attention in recent years. Besides, several selenium-involved alkyne reactions, especially the alkyne cyclization reactions, have also been realized.…”

Poly(ethylene glycol) Dimethyl Ethers (PEGDME): Efficient and Recyclable Solvents for Aryne-Involved Reactions

“…16 A three-component aminoselenation of aryne 2 using N,Ndimethyl aniline 16 and phenyl selenium bromide 17 gave 2aminophenyl selenium analogue 18 in 75% yield (Scheme 3b). 17 1,2-Aminohalogination of arynes with N,N-dimethyl aniline 16 and CCl4 in PEGDME resulted 20 in 96% yield (Scheme 3c). 18 Synthesis of phenyl piperidine-1-carbodithioate 23 was also attempted as another example of multi-component reaction.…”

“…1 HN-Methyl-N-phenyl-2-(phenylselanyl)aniline (18)17 General procedure A: Compound 16 (100 mg, 0.82 mmol, 1.0 equiv. ), 17 (292 mg, 1.23 mmol, 1.5 equiv.…”

Synthesis of Stannylated Aryl Imines and Amines via Aryne Insertion Reactions into Sn−N Bonds

“…Note that the latter two processes do not rely on direct σ‐bond insertion reactions. Moreover, various methods for the construction of C−N and C−Sn bonds involving aryne intermediates are known [31–39] …”

“…Moreover, various methods for the construction of CÀ N and CÀ Sn bonds involving aryne intermediates are known. [31][32][33][34][35][36][37][38][39] Inspired by our previously reported stannylphosphanylation of aryne intermediates that uses stannylated phosphanes as reagents, [31] we herein report a practical method to implement an N-substituent to an aryl compound along with a stannyl moiety in ortho position via aryne insertion into the NÀ Sn bond of a stannylated imine (Scheme 1C). Notable features of the novel method are: a) the imine functionality installed serves as a protecting group and the free anilines are readily obtained upon simple hydrolysis; b) the simultaneously formed ortho-Snaryl bond has a large synthetic value which is documented by several follow-up reactions showing the diversity that can be achieved by using this approach.…”