中国科学院上海有机化学研究所魏音研究小组，通过两性离子π-炔丙基钯物种与苯并富烯的配体控制的[3+2]/[4+2]环加成反应实现螺茚烯的发散合成。相关论文于2025年3月5日发表于国际顶尖学术期刊《中国化学》杂志上。

通过钯催化两性离子π-丙炔钯与苯并呋喃之间的环加成反应，以中高收率合成了螺轮烯，具有良好的官能团相容性和广泛的底物普遍性。该方案具有高度区域选择性的[3+2]和[4+2]环加成之间的切换过程，由不同咬合角的膦配体控制。通过机理研究和DFT计算明确了反应机理，表明配体与底物的配位方式和配体的咬合角对产物的区域选择性起关键作用。

附：英文原文

Title: A Divergent Synthesis of Spiroindenes via Ligand-Controlled [3+2]/[4+2] Cycloadditions of Zwitterionic π-Propargyl Palladium Species with Benzofulvenes

Author: Yongjie Long, Xianhua Zhong, Min Shi, Yin Wei

Issue&Volume: 2025-03-05

Abstract: A divergent synthesis of spiroindenes through a palladium catalyzed cycloaddition between zwitterionic π-propargyl palladium species and benzofulvenes in moderate to good yields has been disclosed along with good functional group compatibility and a broad substrate universality. This protocol features a highly regioselective switchable process between [3+2] and [4+2] cycloadditions controlled by phosphine ligands with different bite angles. The reaction mechanism has been clarified by mechanistic studies and DFT calculations, rendering that the coordination modes of the ligands with the substrates and the bite angle of the ligands play critical roles in the product regioselectivity.

DOI: 10.1002/cjoc.202401301

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.202401301