铂催化伯膦的对映选择性串联烷基化/芳基化反应。P-手性苊烯膦的不对称合成。

Platinum-catalyzed enantioselective tandem alkylation/arylation of primary phosphines. Asymmetric synthesis of P-stereogenic 1-phosphaacenaphthenes.

作者信息

Anderson Brian J, Guino-o Marites A, Glueck David S, Golen James A, DiPasquale Antonio G, Liable-Sands Louise M, Rheingold Arnold L

机构信息

Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA.

出版信息

Org Lett. 2008 Oct 16;10(20):4425-8. doi: 10.1021/ol801616s. Epub 2008 Sep 23.

DOI:10.1021/ol801616s

PMID:18808136

Abstract

Enantioselective tandem alkylation/arylation of primary phosphines with 1-bromo-8-chloromethylnaphthalene catalyzed by Pt(DuPhos) complexes gave P-stereogenic 1-phosphaacenaphthenes (AcePhos) in up to 74% ee. Diastereoselective formation of four P-C bonds in one pot with bis(primary) phosphines gave C2-symmetric diphosphines, including the o-phenylene derivative DuAcePhos, for which the rac isomer was formed with high enantioselectivity. These reactions, which appear to proceed via an unusual metal-mediated nucleophilic aromatic substitution pathway, yield a new class of heterocycles with potential applications in asymmetric catalysis.

摘要

由铂（双膦）配合物催化的伯膦与1-溴-8-氯甲基萘的对映选择性串联烷基化/芳基化反应，可得到对映体过量高达74%的P-手性苊烯膦（AcePhos）。使用双（伯）膦在一锅反应中通过非对映选择性形成四个P-C键，可得到C2对称双膦，包括邻亚苯基衍生物双苊烯膦（DuAcePhos），其外消旋体以高对映选择性形成。这些反应似乎通过一种不寻常的金属介导的亲核芳香取代途径进行，产生了一类在不对称催化中具有潜在应用的新型杂环化合物。