Reichl Stephan, Balázs Gábor, Scheer Manfred
Institute of Inorganic Chemistry, University Regensburg Universitätsstraße 31 93053 Regensburg Germany
Chem Sci. 2023 Mar 13;14(14):3834-3838. doi: 10.1039/d3sc00580a. eCollection 2023 Apr 5.
A novel synthetic route for (parent) phosphorus-containing cycloalkanes such as phosphetanes, phospholanes, phosphinanes and phosphepanes is reported. By using [K(dme)][CpFe(η-P)] (I) in combination with α,ω-dibromoalkanes C H Br [ = 3-6], unique phosphetane, phospholane, phosphinane and phosphepane precursor complexes [CpFe{η-P(CH) }] [ = 3-6] (2-5) are synthesised. They act as P-atom carriers and the corresponding phosphetane, phospholane, phosphinane and phosphepanes (6-9) can be released by nucleophiles , potassium benzyl (KBn) or LiAlH. The latter enables the selective synthesis of parent cyclic secondary phosphines (10) in an easy and straightforward way, including the first parent phospholane (10b).
报道了一种用于制备(母体)含磷环烷烃(如磷杂环丁烷、磷杂环戊烷、磷杂环己烷和磷杂环庚烷)的新型合成路线。通过将[K(dme)][CpFe(η-P)](I)与α,ω-二溴代烷烃CₙH₂ₙBr₂[n = 3 - 6]联用,合成了独特的磷杂环丁烷、磷杂环戊烷、磷杂环己烷和磷杂环庚烷前体配合物[CpFe{η-P(CH₂)ₙ}] [n = 3 - 6](2 - 5)。它们作为磷原子载体,相应的磷杂环丁烷、磷杂环戊烷、磷杂环己烷和磷杂环庚烷(6 - 9)可通过亲核试剂、苄基钾(KBn)或LiAlH₄释放出来。后者能够以简便直接的方式选择性合成母体环状仲膦(10),包括首例母体磷杂环戊烷(10b)。