Synthesis of in,out-isomeric phosphite and phosphate cryptands

Abstract

The reaction of POCl 3 with the trinuclear bisphenol 1 has been investigated. All three homeomorphic in,out-isomers of the phosphorus cryptand were isolated. Among them the out,out-isomer was the main macrobicyclic product obtained. The reaction of the previously described in,in-phosphite 2 with CuCl afforded an interesting complex containing two metal centers bridging the cavity of the cryptand together with a central chloride ion. This complex suggested the use of Cu(I) as a template for the formation of the formerly described in,outphosphite cryptands. With this method it is now possible to carry out the reaction in higher concentrated solution to isolate larger quantities of the phosphorus macrobicycles.

Molecules that Turn Themselves Inside‐Out: Tuning in/out Equilibria and Homeomorphic Isomerization in Macrobicyclic Dibridgehead Diphosphines P((CH2)n)3P Newly Accessible by Earth‐Abundant‐Metal Templates

“…Although it was not possible to quantify equilibria and dynamic behavior, they anticipated many of the phenomena described in this study. Interestingly, with triarylphosphine and triarylphosphate bridgeheads, they observed the same upfield/downfield out / in 31 P{ 1 H} NMR relationships as we do in Figure 3 [11c] …”