FUNCTIONALIZED PHOSPHINES: SYNTHESIS,REACTIVITY AND TRANSITION METAL CHEMISTRY

Ten-membered heterocycles of the type PhN(PCl₂){OC₆H₂(R)₂ (μ-S(CH₂))((R)₂─C₆H₂O─)} (R = Me, ⁱPr or ^tBu) have been prepared and their transition metal chemistry is explored. Functionalised phosphines react with transition metals to give interesting metallacycles. Several Group 6, ruthenium, platinum metals and novel titanium(IV) metallacycles have been structurally characterized.     

Book Review

Abstract

A Guide to Organophosphorus Chemistry, by Louis D. Quin, an internationally recognized authority, published by John Wiley and Sons (http://www.wiley.com/chemistry) ISBN 0-471-31824-8, $94.95, 394pp.

Aminophosphonic and Aminophosphinic Acids: Chemistry and Biological Activity. Editors: Valery P. Kukhar (Ukrainian Academy of Sciences) and Harry R Hudson (University of North London). Published by John Wiley and Sons Ltd., Chichester, UK, on 31 March, 2000. ISBN 0 471-89149-5, 175.00 Pounds sterling, 634 pages.

Phosphorus Ylides. Chemistry and Application in Organic Synthesis, by Oleg I. Kolodiazhnyi. Published by Wiley-VCH, 1999, ISBN 3-527-29531-3, 220SF, 555 pages.     

Stacking-Conformations in Functionally Substituted Phosphines

The methods of synthesis and space structure of phosphorus-containing compounds, in which stacking conformation is realized, are considered. It is shown that intramolecular stacking can be observed in monoheterocyclic compounds, bi-and polycyclic compounds, complexes of metals and acyclic compounds.     

Spectral Assignment of Phenanthrene Derivatives Based on 6H-Dibenzo[C,E][1,2] Oxaphosphinine 6-Oxide by NMR and Quantum Chemical Calculations

Abstract

Organophosphorus compounds such as 6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide (DOPO, 1) and its derivatives are important and versatile compounds for a broad field of applications. However, a thorough spectral assignment is often subordinate to its chemical properties. This article presents and unambiguously attributes the ¹H and ¹³C NMR spectra of DOPO (1), selected products yielded from the Atherton–Todd reaction (2–4), DOPO-HQ (5) as well as sulfur derivatives (6–7) via a set of 1D- and 2D-NMR experiments. The complex P-C and P-H coupling patterns are discussed and compared with the derivatives possessing different chemical environments around the phosphorus atom. In addition, we compared our results with density functional theory calculations. Even though the prediction of NMR data of organophosphorus compounds via molecular modeling is limited, this study presents a method that yields good results for this class of heterocycles. This knowledge should help to quickly assign NMR spectroscopic data of other DOPO (1) derivatives and can be extrapolated to organophosphorus compounds in general.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: NMR Spectra of Compounds 1-7 (Figures S1 - S15).     

Versatile Cycloaddition Reactions of 1-Alkyl-1,2-Diphospholes

Abstract

The reactivity of 1-alkyl-1,2-diphospholes in cycloaddition reactions with dienes, dienophiles or 1,3-dipoles was examined. 1-Alkyl-1,2-diphospholes (2 ) exhibit dual reactivity and act as diene toward maleic acid derivatives or as dienophiles with 2,3-dimethyl-1,3-butadiene. The 1-alkenyl-1,2-diphospholes (4 ) are readily involved in intramolecular [4 + 2] cycloaddition reactions leading to cage phosphines (5 ). Interaction of 1-alkyl-1,2-diphospholes (2) with 1,3-dipolar reagents (diphenyldiazomethane and nitrones) results in formation of the bicyclic phosphiranes (8) and dimers of 1-alkyl-1,2-diphosphole oxides (9) or bicyclic phosphine oxides (10) with a β-lactam moiety depending on temperature.