16079-17-7Relevant articles and documents
Rhodium-Catalyzed [5+2] Cycloaddition of 3-Acyloxy-1,4-enyne with Alkene or Allene
Song, Wangze,Lynch, John C.,Shu, Xing-Zhong,Tang, Weiping
, p. 2007 - 2011 (2016)
We recently developed a completely new type of Rh-catalyzed [5+2] cycloaddition by using 3-acyloxy-1,4-enyne (ACE) as the 5-carbon building block. In this update, we show that ACE can undergo intramolecular [5+2] cycloaddition with either an alkene or an allene in the presence of an appropriate rhodium catalyst and ligands to afford bicyclic compounds with multiple stereogenic centers. In most cases, cis-fused bicyclo[5.3.0]decadienes are prepared highly diastereoselectively. (Figure presented.) .
Regioselective Synthesis of Multifunctional Allylic Amines; Access to Ambiphilic Aziridine Scaffolds
McLaughlin, Mark G.,Roberts, Dean D.
supporting information, p. 4463 - 4467 (2021/06/28)
We describe, for the first time, a highly regioselective hydrosilylation of propargylic amines. The reaction utilizes a PtCl2/XantPhos catalyst system to deliver hydrosilanes across the alkyne to afford multifunctional allylic amines in high yields. The reaction is tolerant to a wide variety of functional groups and provides high value intermediates with two distinct functional handles. The synthetic applicability of the reaction has been shown through the synthesis of diverse ambiphilic aziridines.
Mechanistic Insights into the Ru(II)-Catalyzed Intramolecular Formal [3 + 2] Cycloaddition of (E)-1,6-Enynes
Liu, Rui,Chou, Yajie,Lian, Bing,Fang, De-Cai,Gao, Ming,Cheng, Tanyu,Liu, Guohua
supporting information, p. 6815 - 6820 (2019/09/30)
Design of a unique reaction pathway in transition-metal-catalyzed 1,6-enynes cyclization to construct valuable synthetic motifs is a significant challenge in organic chemistry. Herein, we report a Ru(II)-catalyzed formal [3 + 2] cycloaddition as an efficient method to prepare unprecedented bicyclo[3.3.0]octenes from readily available (E)-1,6-enynes. Mechanistic studies based on the deuterium labeling experiments and the DFT calculation disclose a reasonable mechanistic pathway, where a ruthenacyclopentene generated by an ene-yne oxidative cyclization undergoes a sequential ?-hydride elimination and intramolecular hydroruthenation to form a ruthenacyclohexene, producing the desirable bicyclo[3.3.0]octenes.