ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Reactions of Magnesium-Cyclooctatetraene with Dichlorophosphanes: Characterization and RearrangementsThe reaction of magnesium-cyclooctatetraene (MgCOT) with dichlorophosphanes RPCl2 (R = tert-butyl, cyclohexyl, menthyl) yields 9-phosphabicyclo[6.1.0]nonatrienes 1b-d, which thermally rearrange to syn-9-phosphabicyclo[4.2.1]nonatrienes 2b-d. However, 1b and c also rearrange via electrocyclic ring opening and intramolecular [4 + 2] cyclization to trans-dihydrophosphindoles 3b and c. The rearrangement of 1 in the presence of Ni0 catalysts or photochemically was found to give the corresponding epimeric products 4 of the thermally induced process. With RPCl2 (R = OR, NR2) and MgCOT, the syn-9-phosphabicyclo[4.2.1]nonatrienes 2e, f are obtained directly.
Notes:
Die Umsetzung von Magnesium-Cyclooctatetraen (MgCOT) mit Dichlorphosphanen RPCl2 (R = tert-Butyl, Cyclohexyl, Menthyl) liefert 9-Phosphabicyclo[6.1.0]nonatriene 1b-d, die thermisch zu syn-9-Phosphabicyclo[4.2.1]nonatrienen 2b-d umlagern. Zusätzlich lagern 1b und c nach elektrocyclischer Ringöffnung und intramolekularer [4 + 2]-Addition zu trans-Dihydrophosphindolen 3b und c um. In Gegenwart von Ni0-Verbindungen oder photochemisch lagern die Verbindungen 1 zu den zu 2 epimeren anti-Verbindungen 4 um. Mit RPCl2 (R = OR, NR2) und MgCOT erhält man die syn-9-Phosphabicyclo[4.2.1]nonatriene 2e und f unmittelbar.
Additional Material:
4 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19851180110
