104358-27-2Relevant academic research and scientific papers
Glaser-Hay hetero-coupling in a bimetallic regime: A Ni(II)/Ag(i) assisted base, ligand and additive free route to selective unsymmetrical 1,3-diynes
Mohanty, Anuradha,Roy, Sujit
supporting information, p. 10796 - 10799 (2017/10/06)
A Ni(OAc)2/Ag(OTf) catalysed coupling of aryl alkynes and propargylic alcohol/ether/ester gave the corresponding unsymmetrical 1,3-diynes in good to excellent yields. The reaction does not require bases, ligands or additives and shows excellent hetero-selectivity, thereby addressing the current challenges in the field of coupling of two different terminal alkynes.
Benzannulation of triynes to generate functionalized arenes by spontaneous incorporation of nucleophiles
Karmakar, Rajdip,Yun, Sang Young,Chen, Jiajia,Xia, Yuanzhi,Lee, Daesung
supporting information, p. 6582 - 6586 (2015/06/02)
The thermal reaction of ester-tethered 1,3,8-triynes provides novel benzannulation products with concomitant incorporation of a nucleophile. Evidence suggests that this reaction proceeds via an allene-enyne intermediate generated by an Alder-ene reaction in the first step. Depending on the substituent of the alkyne moiety on the allene-enyne intermediate, the subsequent transformation can take one of two different paths, each leading to discrete aromatization products. The benzannulation of a silane-substituted 1,3,8-triynes provides arene products with a nucleophile incorporated onto the newly formed benzene core, whereas an aryl substituent leads to nucleophile trapping at the benzylic carbon atom connected to the aryl substituent. The formation of these two different products results from the involvement of two regioisomeric allene-enyne intermediates.
Optimization of solid-supported Glaser-Hay reactions in the microwave
Lampkowski, Jessica S.,Maza, Johnathan C.,Verma, Sanjana,Young, Douglas D.
, p. 5276 - 5285 (2015/05/13)
The translation of organometallic reactions into a microwave reactor has numerous advantages. Herein, we describe the application of a previously developed solid-supported Glaser-Hay reaction to microwave conditions. Overall, an array of diynes has been prepared demonstrating the ability to conduct chemoselective reactions in the microwave within 20 min compared to the 16 h thermal conditions. Moreover, non-microwave transparent alkynes have been found to react more quickly, preventing catalyst quenching, and resulting in higher yields.
Preparation of asymmetrical polyynes by a solid-supported Glaser-Hay reaction
Lampkowski, Jessica S.,Durham, Corinn E.,Padilla, Marshall S.,Young, Douglas D.
supporting information, p. 424 - 427 (2015/02/05)
Polyynes exhibit both unique photophysical properties and biological activities, necessitating efficient syntheses towards these core structures. A novel methodology for the construction of highly conjugated asymmetrical polyynes has been developed in a chemoselective fashion utilizing a solid-support. The synthesis has been applied to prepare a small library of polyynes in good to moderate yield. Moreover, their interesting fluorescence properties have been investigated, demonstrating the ability to tune fluorescence through selection of appropriate synthetic building blocks. This journal is
Development of solid-supported Glaser-Hay couplings
Tripp, Valerie T.,Lampkowski, Jessica S.,Tyler, Ryan,Young, Douglas D.
supporting information, p. 164 - 167 (2014/05/06)
While the Glaser-Hay coupling of terminal alkynes is a useful reaction, several issues associated with chemoselectivity preclude its widespread application in synthetic chemistry. To address these issues, a solid-supported Glaser-Hay methodology was developed to afford only asymmetric diyne products. This methodology was then applied to a series of immobilized alkynes with a diverse set of soluble alkynes to generate an array of heterocoupled products in high yields and purities.
