Organophosphorus Chemistry

Volume 46

David W Allen, David Loakes, John C Tebby

• Publisher: Royal Society of Chemistry
• Year: 2017
• Edition: 1
• eBook ISBN:
  9781788011570
• Topic: Physical Sciences
• Subtopic: Organic Chemistry

Coverage in this annual review of the literature presents a comprehensive and critical survey of the vast field of study involving organophosphorus compounds, from phosphines and phosphonium salts through to phosphorus acids, nucleotides, ylides and phosphazenes. The Editors have added to the usual content with a timely chapter on the recent developments in green synthetic approaches in organophosphorus chemistry to reflect current interests in the area.

Quinquevalent phosphorus acids

Piotr Bałczewski^a,b and Joanna Skalik^a

DOI: 10.1039/9781788010689-00213

^a Polish Academy of Sciences, Centre of Molecular and Macromolecular Studies, Sienkiewicza 112, 90-363 Łódź, Poland.
E-mail: [email protected][email protected]

^b Jan Długosz University in Częstochowa, Armii Krajowej 13/15, 42-200 Częstochowa, Poland

1 Introduction

This chapter covers scientific contributions in quinquevalent organophosphorus chemistry published in the literature in 2015. The review is not comprehensive but shows some of the significant achievements in this area contained in leading journals. The chapter describes compounds possessing three P–O bonds (phosphates), two P–O and one P–C bonds (phosphonates) as well as one P–O and two P–C bonds (phosphinates) in addition to the phosphoryl group P=O. Each of the main sections has been divided in the same way, covering synthesis, reactions and biological aspects of phosphoric, phosphonic and phosphinic acids and their derivatives. As in previous years, an additional subsection devoted to miscellaneous applications, other than biological ones, have been added in two sections devoted to phosphates and phosphonates.

In some cases, syntheses and reactions have been carried out simultaneously on two groups of compounds (e.g. phosphonates and phospinates), however they are referred to only once in one subsection. The interest in chemistry of phosphoric and phosphonic acids and their derivatives has maintained in the review period while the interest in the area of phosphinic acids and their derivatives has decreased this year.

On the same level, as in the previous year papers on the use of chiral phosphoric acids has remained the same. This subsection was introduced in 2009, however, due to limited space, the achievements in this area are mentioned but not discussed in detail in this year. Chiral phosphoric acids as catalysts found applications in various organic reactions involving as examples: Mannich-type addition of azlactones with aldimines, Michael addition of unactivated α-substituted ketones, enantioselective Diels–Alder reaction of α-substituted acroleins with 1,2-dihydropyridines, asymmetric carbozincation of pentafulvenes, asymmetric hydrohydroxyalkylation of butadiene, imine hydrogenation with Knçlker's iron complex, allylboration-Heck reaction of 2-bromobenzaldehydes with allylboronic acid pinacol ester, [4+2] hetero-Diels–Alder reaction of ortho-quinone methides and unactivated alkenes, cyclisation reactions of β,γ-unsaturated α-ketoesters, arylamines and acetylacetone, dearomatising redox cross coupling aryl hydrazines and ketones, asymmetric β-hydrogen transfer reduction of α-trifluoromethyl ketones, conversion of an indenyl cyclobutanol to spirocyclic indene and many others.

Other aspects, like total syntheses of biologically active compounds utilising phosphates, have been reported during the review period, including the total syntheses of (+)-leustroducsin B and (−)-enigmazole A, an asymmetric total synthesis of the (3R,16Z,20E,23R)-(−)-eushearilide via Wittig/aldol/macrolactonisation reaction sequence, a synthesis of a phosphonooxymethyl prodrug of the antitumor agent triptolide, prepared from a natural product, a highly stereoselective total syntheses of cephalosporolide E and cephalosporolide F, which was transformed into the cephalosporolide E via a stereocontrolled spiroketal isomerisation, promoted by diphenylphosphate acid.

The total syntheses of biologically active compounds utilising phosphonates as reagents have also been intensly developed as in previous years and included for instance: a total synthesis of topsentolide A1 and its stereoisomers, a cytotoxic oxylipin against human solid tumor cell lines, a total synthesis of the natural products (−)-cedarmycins A and B utilising synthesis of α-alkylidene-γ-butyro...

Table of contents

• Cover
• Title
• Copyright
• Contents
• Preface
• Phosphines and related C–P bonded compounds
• Tervalent phosphorus acid derivatives
• Phosphine chalcogenides
• Phosphonium salts and P-ylides
• Nucleotides and nucleic acids: mononucleotides
• Quinquevalent phosphorus acids
• Pentacoordinated and hexacoordinated compounds
• Phosphazenes
• Green synthetic approaches in organophosphorus chemistry: recent developments