Phosphine-Catalyzed Aryne Oligomerization: Direct Access to α,ω-Bisfunctionalized Oligo(ortho-arylenes)

A phosphine-catalyzed oligomerization of arynes using selenocyanates was developed. The use of JohnPhos as a bulky phosphine is the key to accessing alpha,omega-bisfunctionalized oligo(ortho-arylenes) with RSe as the substituent at one terminus and CN as the substituent at the other. The in situ formation of R3PSeR' cations, serving as sterically encumbered electrophiles, hinders the immediate reaction that affords the 1,2-bisfunctionalization product and instead opens a competitive pathway leading to oligomerization. Various optimized conditions for the predominant formation of dimers, but also for higher oligomers such as trimers and tetramers, were developed. Depending on the electronic properties of the electrophilic reaction partner, even compounds up to octamers were isolated. Optimization experiments revealed that a properly tuned phosphine as catalyst is of crucial importance. Mechanistic studies demonstrated that the cascade starts with the attack of cyanide; aryne insertion into n-mers leading to (n+1)-mers was ruled out.

Automated summary

A phosphine-catalyzed oligomerization of arynes using selenocyanates has been developed to access alpha, omega-bisfunctionalized oligo(ortho-arylenes). The use of JohnPhos as a bulky phosphine catalyst is crucial for this reaction to occur. Various optimized conditions have been established to predominantly form dimers, but also higher oligomers, up to octamers, depending on the electronic properties of the electrophilic reaction partner. Mechanistic studies show that the cascade reaction starts with cyanide attack and rules out aryne insertion into n-mers leading to (n+1)-mers.