Asymmetric Intermolecular Cobalt-Catalyzed Pauson–Khand Reaction Using a P‑Stereogenic Bis-phosphane

The asymmetric intermolecular and
catalytic Pauson–Khand
reaction has remained an elusive goal since Khand and Pauson discovered
this transformation. Using a novel family of P-stereogenic phosphanes,
we developed the first catalytic system with useful levels of enantioselection
for the reaction of norbornadiene and trimethylsilylacetylene. The
results demonstrate that Co–bisphosphane systems are sufficiently
reactive and that they lead to high selectivity in the intermolecular
process.

自坎德（Khand）与帕库斯（Pauson）发现该转化反应以来，不对称分子间催化帕库斯-坎德反应（Pauson–Khand reaction）一直是一个极具挑战性的目标。本研究依托一类全新的P手性膦配体（P-stereogenic phosphanes），开发出首个对降冰片二烯与三甲基硅基乙炔的反应具有实用级对映选择性的催化体系。研究结果表明，钴-双膦配体体系（Co–bisphosphane systems）具备足够的反应活性，且可在分子间反应中实现高选择性。