19171-57-4

Upstream product

• 603-35-0 triphenylphosphine 
• 3878-44-2 Triphenylphosphine selenide 
• 2526-64-9 dichlorotriphenylphosphorane 
• 791-28-6 Triphenylphosphine oxide 
• 3878-45-3 triphenylphosphine sulfide 
• 7719-09-7 thionyl chloride 

Downstream Products

• 142781-10-0 C₂₂H₂₅O₃P₂S⁽¹⁺⁾*Cl^(1-) 
• 16843-32-6 {(C₆H₅)3PCl}⁽¹⁺⁾*{BCl₄}^(1-)={(C₆H₅)3PCl}{BCl₄} 
• 791-28-6 Triphenylphosphine oxide 
• 1319713-01-3 C₂₄H₂₆OP⁽¹⁺⁾*Cl^(1-) 
• 2049-55-0 triphenylphosphine borane 
• 603-35-0 triphenylphosphine 
• 2001-45-8 tetraphenyl phosphonium chloride 
• 515-40-2 neophyl chloride 
• 13371-17-0 butyltriphenylphosphonium chloride 
• 896-33-3 ethyltriphenylphosphonium chloride 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 814-49-3 diethyl chlorophosphate 
• 2524-04-1 diethyl phosphorochloridothioate 
• 3878-45-3 triphenylphosphine sulfide 

Relevant academic research and scientific papers

Synthesis of glycosyl chlorides using catalytic Appel conditions

The stereoselective synthesis of glycosyl chlorides using catalytic Appel conditions is described. Good yields of α-glycosyl chlorides were obtained using a range of glycosyl hemiacetals, oxalyl chloride and 5 mol% Ph3PO. For 2-deoxysugars treatment of the corresponding hemiacetals with oxalyl chloride without phosphine oxide catalyst also gave good yields of glycosyl chloride. The method is operationaly simple and the 5 mol% phosphine oxide by-product can be removed easily. Alternatively a one-pot, multi-catalyst glycosylation can be carried out to transform the glycosyl hemiacetal directly to a glycoside.

On the reaction of triphenylphosphane with thionyl chloride

Triphenylphosphine reacts with thionyl chloride to give [Ph 3PCl]Cl, Ph3PO and Ph3PS the formation of the anions S(O)Cl and SCl being discussed; the crystal structure of [Ph 3PCl]Cl·S(O)Cl2 is reporte

Direct evidence of a multicentre halogen bond: Unexpected contraction of the P-XXX-P fragment in triphenylphosphine dihalides

Triphenylhalophosphonium halides, Ph3PX2, form crystals comprising bridged linear cations [Ph3P-X-X-X-PPh 3]+ where the X3 bridge is shortened from 6.56 A in Cl-Cl-Cl to 6.37 A in the Br-Br-Br system. It is proposed that this structure is stabilised by five-centre/six-electron (5c-6e) hypervalent interactions.

Saccharin Aza Bioisosteres - Synthesis and Preclinical Property Comparisons

Saccharin is a well-known scaffold in drug discovery. Herein, we report the synthesis and preclinical property comparisons of three bioisosteres of saccharin: aza-pseudosaccharins (cluster B), and two new types of aza-saccharins (clusters C and D). We dem

A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts

The metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum chemical calculations support the attack of the dissociated chloride anion of intermediated phosphonium salt at the silicon of the disilane as the rate-limiting step for deprotection. The exquisite purity of the resultant phosphine(III) ligands after the simple removal of volatiles under reduced pressure circumvents laborious purification prior to metalation and has permitted the facile formation of important transition metal catalysts.

Long sought synthesis of quaternary phosphonium salts from phosphine oxides: Inverse reactivity approach

Quaternary phosphonium salts (QPS), a key class of organophosphorus compounds, have previously only been available by routes involving nucleophilic phosphorus. We report the realisation of the opposite approach to QPS utilising phosphine oxides as the electrophilic partner and Grignard reagents as nucleophiles. The process is enabled through the crucial intermediacy of the derived halophosphonium salts. The route does not suffer from the slow kinetics and limited availability of many parent phosphines and a broad range of QPS were prepared in excellent yields.

Hypervalent Iodine-Based Activation of Triphenylphosphine for the Functionalization of Alcohols

The use of hypervalent iodine reagents as a general tool for the activation of PPh 3 and its application to the functionalization of alcohols is reported. Combination of PPh 3 with PhICl 2 or TolIF 2 gives dihalophosphoranes that are characterized by 31 P NMR, however, with PhIOAc 2, PhI(OTFA) 2, or the cyclic chloro(benzoyloxy)iodane, no phosphoranes were observed. Reaction of these iodanes with PPh 3 in the presence of primary, secondary, or tertiary alcohols results in either halogenation or acyl-transfer products in moderate to high yield.

Lithium Borohydride for Achiral and Stereospecific Reductive Boronation at Phosphorus: Lack of Electronic Effects on Stereoselective Formation of Alkoxyphosphonium Salts

We report LiBH4 as a preferred, simple and effective reagent for reductive boronation of achiral and racemic chlorophosphonium salts (CPS) and for diastereomeric alkoxyphosphonium salts (DAPS), both of which are, in turn, easily generated from either the corresponding phosphane or, more conveniently, the phosphane oxide. Further, we have shown that the DAPS reduction/boronation could be achieved with complete stereocontrol to give scalemic phosphane-borane directly in excellent yield and enantiomeric excess (ee). This new methodology was employed to investigate the effects of aryl substitution on the outcome of dynamic kinetic resolution of arylmethylphenylphosphanes and phosphane oxides via DAPS. It was found that substitution at the ortho position strongly affects the degree of stereoselection. However, surprisingly, we confirmed that there was no variation of stereoselectivity seen with the electronic effect of substituents on the para position.

Systematic survey of positive chlorine sources in the asymmetric Appel reaction: Oxalyl chloride as a new phosphine activator

A wide selection of phosphine activators has been screened to improve the selection process in the asymmetric Appel reaction. Of the activators screened, hexachloroacetone (HCA) gave the highest selectivity with excellent yield, but at least one of its by

Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride

A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.