Durham Austin C, Liu Cindy R, Wang Yi-Ming
Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, 15213, Pittsburgh, PA, USA.
Chemistry. 2023 Aug 10;29(45):e202301195. doi: 10.1002/chem.202301195. Epub 2023 Jul 12.
Cyclopentadienyliron dicarbonyl-based complexes present opportunities for underexplored disconnections in synthesis. Access to challenging dihydropyrrolone products is achieved by propargylic C-H functionalization of alkynes for the formation of cyclic organoiron species. Excellent regioselectivity for unsymmetrical alkynes is observed in many cases. Notably, regioselectivity under these stoichiometric conditions diverges from those observed previously under catalysis, occurring at the more-substituted terminus of the alkyne, allowing for methine functionalization and the formation of quaternary centers. Divergent demetallation of the intermediate organoiron complexes gives access to chemically diverse products which are amenable to further functionalization.
基于环戊二烯基铁二羰基的配合物为合成中未充分探索的断键反应提供了机会。通过炔烃的炔丙基C-H官能化反应形成环状有机铁物种，从而获得具有挑战性的二氢吡咯酮产物。在许多情况下，对于不对称炔烃都观察到了优异的区域选择性。值得注意的是，这些化学计量条件下的区域选择性与之前在催化条件下观察到的不同，发生在炔烃取代较多的末端，从而实现次甲基官能化并形成季碳中心。中间体有机铁配合物的不同脱金属反应可得到化学性质多样的产物，这些产物易于进一步官能化。
