Search

Tertiary α-hydroxyphosphine oxides have been synthesized via the catalyst- and solvent-free reaction between available secondary phosphine oxides and aliphatic, aromatic and heteroaromatic ketones at 20–62 °C in near to 96–98% yield. The developed method meets the requirements of green chemistry and the PASE (pot, atom, step economy) paradigm. According to quantum-chemical calculations at the B3LYP/6-311++G(d,p) level, the synthesized hydroxyphosphine oxides feature a weak (≈3 kcal·mol–1) O−H···O=P intramolecular hydrogen bond. [ABSTRACT FROM AUTHOR]

The catalyst- and solvent-free reaction between bis(fluoroalkyl) phosphonates and aldimines occurs under mild conditions (20–22 °C, 0.25–4 h) to afford a new family of α-amino polyfluoroalkylphosphonates in up to quantitative yields. [ABSTRACT FROM AUTHOR]

Traditional methods for C-P bond formation via direct addition of P-H species to unsaturated compounds are usually implemented in the presence of base and metal catalysts or radical initiators in various organic solvents. During the last five years, a novel efficient and general catalyst/initiator- and solvent-free version of the hydrophosphination and hydrophosphinylation of multiple C-C bonds with H-phosphines and their chalcogenides has begun to develop and it is attracting growing attention. This approach corresponds to the recently emerged pot-, atom-, and step-economy (PASE) green paradigm. This review covers the literature on the synthesis of useful and in-demand organophosphorus compounds via catalyst- and solvent-free addition of P-H species to alkenes and alkynes. 1 Introduction 2 Addition of Secondary Phosphines to Alkenes 3 Hydrophosphinylation of Alkenes with Secondary Phosphine Chalcogenides 3.1 Oxidative Addition of Phosphine Oxides to Vinyl Sulfides 3.2 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Alkenes 3.3 Addition of Secondary Phosphine Sulfides and Phosphine Selenides to Divinyl Chalcogenides 3.4 Hydrophosphinylation of Alkenes with Secondary Phosphine/Chalcogen Pair (Three-Component Reactions) 4 Addition of Secondary Phosphines to Alkynes 5 Addition of Secondary Phosphine Chalcogenides to Alkynes 6 Conclusion. [ABSTRACT FROM AUTHOR]

The original four-component reaction between secondary phosphines, primary amines, aldehydes, and elemental sulfur or selenium occurs chemoselectively under mild conditions (60 °C, benzene, 3–9 h) to afford the hitherto unknown functionalized α-aminophosphine sulfides and selenides in good to excellent yields. [ABSTRACT FROM AUTHOR]

An efficient catalyst- and solvent-free method for the synthesis of tertiary a-hydroxyphosphine chalcogenides, via the almost quantitative addition of secondary phosphine chalcogenides to diverse aldehydes under mild conditions (20-52 °C, from 10 min to 5 h), is reported. [ABSTRACT FROM AUTHOR]

The addition of secondary phosphine sulfides and selenides to alkynes proceeds readily (80 °C, 5-13 h) without catalysts or solvents to afford regio- and stereoselectively anti-Markovnikov adducts as tertiary alkenylphosphine chalcogenides of Z-configuration, in 60- 94% yield. [ABSTRACT FROM AUTHOR]

Under catalyst- and solvent-free conditions, secondary phosphine selenides easily add to diverse alkenes [acrylonitrile, allyl alcohol, styrene, vinyl ethers, vinyl sulfides, and trimethyl(vinyl) silane] at 80 °C (3-20 h) to give anti-Markovnikov adducts in 70-95% yield. [ABSTRACT FROM AUTHOR]

A one-pot, atom-economic, metal- and halogen-free synthesis of functional triphosphines with nitrogen and (or) oxygen atoms as additional weaker coordinating sites (new hemilabile ligands) through exhaustive addition of secondary phosphines to available trivinyl ethers of aminotriols and triols has been developed. The reaction proceeds under free-radical conditions (UV irradiation or AIBN, with 3:1 reactant molar ratio) to give chemo- and regioselectively anti-Markovnikov triadducts to all three vinyloxy groups in good to excellent yields. [ABSTRACT FROM AUTHOR]

Secondary phosphines and phosphine chalcogenides add to the divinyl ether of α,ω-alkane diols regio- and chemoselectively under free-radical conditions (UV irradiation or AIBN, 2:1 reactants molar ratio) to give anti-Markovnikov diadducts in good to excellent yields (65-98%). [ABSTRACT FROM AUTHOR]

A family of previously unknown phosphinodiselenoic esters containing a selenoacetal moiety, R² 2P(=Se)SeCH(Me)OR¹ (R¹, R² = alkyl, aryl, etc.), were synthesized by means of a three-component reaction between the elemental selenium and the corresponding vinyl ether and secondary phosphine. The reaction proceeds readily in 1,4-dioxane at 90 °C for 1-1.5 hours and gives the phosphinodiselenoic esters quantitatively and in an entirely atomeconomic manner. The reaction proceeds through electrophilic addition to the electron-rich double bond of the phosphinodiselenoic acids generated in situ. [ABSTRACT FROM AUTHOR]

Oxidative transition-metal-free, cross-coupling reaction between secondary phosphine chalcogenides and alcohols or phenols proceeds in the carbon tetrachoride/triethylamine system under mild conditions (20-52 °C, 1-12 h) to give phosphinochalcogenoic O-esters in 70-95% yields. [ABSTRACT FROM AUTHOR]

Alkali metal diselenophosphinates R1 2PSe2 = aryl, arylalkyl, hetarylalkyl; M = Na, K, or Cs) readily react with organic halides R1 = aryl, arylalkyl, hetarylalkyl; M = Na, K, or Cs) readily react with organic halides R2Hal (R2 = alkyl, allyl, propargyl, benzyl; Hal = Cl, Br, or I) under mild conditions (EtOH, 50-55 °C, 30 min) to afford the corresponding Se-esters of diselenophosphinic acids R1 2P(Se)SeR2 in high yields (77-95%). [ABSTRACT FROM AUTHOR]