Ye Xiaohan, Peng Haihui, Wei Chiyu, Yuan Teng, Wojtas Lukasz, Shi Xiaodong
Department of Chemistry, University of South Florida, Tampa, FL33620, USA.
Lead Contact.
Chem. 2018 Aug 9;4(8):1983-1993. doi: 10.1016/j.chempr.2018.07.004. Epub 2018 Aug 2.
A gold-catalyzed oxidative coupling of alkynes was developed as an efficient approach for the synthesis of challenging cyclic conjugated diynes (CCD). Compared to the classical copper-promoted oxidative coupling reaction of alkynes, this gold-catalyzed process exhibits a faster reaction rate due to the rapid reductive elimination from the Au(III) intermediate. This unique reactivity thus allowed a challenging diyne macrocyclization to take place in high efficiency. Condition screening revealed a [(-Bu)N][Cl-Au-Cl] salt as the optimal pre-catalyst. Macrocycles with ring size between 13 to 28 atoms were prepared in moderate to good yields, which highlighted the broad substrate scope of this new strategy. Furthermore, the synthetic utilities of the cyclic conjugated diynes for copper-free click chemistry have been demonstrated, which showcased the potential application of this strategy in biological systems.
开发了一种金催化的炔烃氧化偶联反应，作为合成具有挑战性的环状共轭二炔（CCD）的有效方法。与经典的铜促进的炔烃氧化偶联反应相比，由于从Au(III)中间体快速还原消除，这种金催化过程表现出更快的反应速率。这种独特的反应活性因此使得具有挑战性的二炔大环化能够高效进行。条件筛选表明[(-Bu)N][Cl-Au-Cl]盐是最佳的预催化剂。制备了环大小在13至28个原子之间的大环，产率适中至良好，这突出了这种新策略广泛的底物范围。此外，还证明了环状共轭二炔在无铜点击化学中的合成效用，展示了该策略在生物系统中的潜在应用。
