193615-06-4

Upstream product

• 111409-79-1 1-bromo-2-(triisopropylsilyl)acetylene 
• 536-74-3 phenylacetylene 
• 591-50-4 iodobenzene 
• 149776-77-2 (Z)-(4-chlorobut-3-en-1-ynyl)triisopropylsilane 
• 181934-30-5 1-[(triisopropylsilyl)ethynyl]-1,2-benziodoxol-3(1H)-one 
• 107474-02-2 1-(triisopropylsilyl)-2-(trimethylsilyl)acetylene 
• 2170-06-1 1-Phenyl-2-(trimethylsilyl)acetylene 
• 89343-06-6 tris-iso-propylsilyl acetylene 

Downstream Products

• 4572-12-7 1,8-diphenylocta-1,3,5,7-tetrayne 

Relevant academic research and scientific papers

Reactivity of 5-(Alkynyl)dibenzothiophenium Salts: Synthesis of Diynes, Vinyl Sulfones, and Phenanthrenes

The reactivity of 5-(alkynyl)dibenzothiophenium salts 1 is explored in the presence of different nucleophiles, dienes, and under photochemical conditions. Reaction with lithium acetylides affords diynes in moderate yields; while depending on the substitution pattern, the reaction with sulfinates delivers either the alkyne transfer products, alkynyl sulfones, or β-(sulfonium) vinyl sulfones through addition to the C?C triple bond. Similar behavior is observed when tosylamines are used as nucleophiles. Salts of general formula 1 also react with dienes to render the corresponding Diels-Alder cycloadducts. The vinyl sulfonium salts obtained by these routes further react with nucleophiles through a Michael addition, dibenzothiophene elimination sequence. Alternatively, they also engage in photoinduced radical cyclizations to produce substituted phenanthrenes. Attempts to use this specific addition/radical cyclization sequence for the construction of the 6a,7-dehydroaporphine skeleton present in several families of alkaloids are also described.

Transition metal-free coupling of terminal alkynes and hypervalent iodine-based alkyne-transfer reagents to access unsymmetrical 1,3-diynes

A variety of unsymmetrical 1,3-diynes can easily be accessed in good yields under catalyst- and transition metal-free conditions by reacting terminal alkynes with hypervalent iodine-based electrophilic alkyne-transfer reagents.

Exploiting the dual role of ethynylbenziodoxolones in gold-catalyzed C(sp)-C(sp) cross-coupling reactions

Reported herein is the gold-catalyzed alkynylation of terminal alkynes using ethynylbenziodoxolones (EBXs), where EBXs serve a dual role as oxidants as well as alkyne transfer agents to access unsymmetrical 1,3-diynes. Hence, the catalytic system requires no external oxidants and is compatible with a broad range of substrates, including those with polar functional groups such as NH, OH and B(OH)2.

Gold-Catalyzed Cadiot–Chodkiewicz-type Cross-Coupling of Terminal Alkynes with Alkynyl Hypervalent Iodine Reagents: Highly Selective Synthesis of Unsymmetrical 1,3-Diynes

A new and efficient method for the synthesis of unsymmetrical 1,3-butadiynes by gold-catalyzed C(sp)–C(sp) cross-coupling of terminal alkynes with alkynyl hypervalent iodine(III) reagents has been developed. The reaction features high selectivity and efficiency, mild reaction conditions, wide substrate scope, and functional-group compatibility, and is a highly attractive complement to existing methods. Mechanistic studies reveal that formation of a phenanthrolinyl-ligated gold(I) complex is crucial for the efficiency and selectivity of the target transformation.

Synthesis of diynes and tetraynes from in situ desilylation/dimerization of acetylenes

(equation presented) An efficient method for the in situ desilylation/oxidative dimerization of (trialkylsilyl)acetylenes is described. This protocol avoids the complications encountered with sensitive diynes by eliminating the deprotection and isolation steps. Various aromatic and alkyl diynes and tetraynes can be synthesized in a straightforward manner in good yields (82-99%) from TIPS-protected acetylenes. This method facilitates the efficient synthesis of novel tetrayne-bridged acetylenic cyclophanes 6 and 7 in a direct manner.