Allylic phosphorus compounds

Allylic phosphorus compounds Tris(tetrabutylammonium) pyrophosphate, 338 Allylsilanes t-Butyllithium, 58 Chlorotrimethylsilane-Lithium, 81 Lithium bis(dimethylphenylsilyl)-cuprate, 161 Methyllithium, 188 Trichlorosilane-t-Amines, 322 Allylic sulfur compounds (Phenylsulfonyl)allene, 247 Sodium benzenesulfinate, 289... 

This is particularly so with a-heterosubstituted derivatives, as shown by a number of recent examples in which oxide derived ylids have been found to give vinyl derivatives in circumstances where the corresponding phosphonate derived ylids do not (2-5). It was therefore decided to prepare the parent (unsubstituted) a-methoxy-allyl phosphorus compounds 1, 2 and 3, in order to investigate their Wittig-type chemistry. 

Carbon-phosphorus bonds are formed by the allylation of various phosphorus compounds. The allyldiphenylphosphine sulfide 346 is formed by the reaction of allylic acetates with lithium diphenylthiophosphide 343[215]. 

Volume F, 21 D.1.5.2.2. Addition of Metalated Allylic Phosphorus and Sulfur Compounds 2071... 

Previous syntheses of terminal alkynes from aldehydes employed Wittig methodology with phosphonium ylides and phosphonates. 6 7 The DuPont procedure circumvents the use of phosphorus compounds by using lithiated dichloromethane as the source of the terminal carbon. The intermediate lithioalkyne 4 can be quenched with water to provide the terminal alkyne or with various electrophiles, as in the present case, to yield propargylic alcohols, alkynylsilanes, or internal alkynes. Enantioenriched terminal alkynylcarbinols can also be prepared from allylic alcohols by Sharpless epoxidation and subsequent basic elimination of the derived chloro- or bromomethyl epoxide (eq 5). A related method entails Sharpless asymmetric dihydroxylation of an allylic chloride and base treatment of the acetonide derivative.8 In these approaches the product and starting material contain the same number of carbons. 

Hydroformylation - [CARBON MONOXIDE] (Vol 5) - [OXO PROCESS] (Vol 17) -of allyl alcohol [ALLYL ALCOHOL AND MONOALLYL DERIVATIVES] (Vol 2) -catalysts for [CATALYSIS] (Vol 5) -C-19 dicarboxylic acids from [DICARBOXYLIC ACIDS] (Vol 8) -of ethylene [ETHYLENE] (Vol 9) -of ethylene [PROPYL ALCOHOLS - N-PROPYLALCOLHOL] (Vol 20) -of maleate and fumarate esters [MALEIC ANHYDRIDE, MALEIC ACID AND FUMARIC ACID] (Vol 15) -phosphine catalyst [PHOSPHORUS COMPOUNDS] (Vol 18) -platinum-group metal catalysts for [PLATINUM-GROUP METALS] (Vol 19) -rhodium catalysis [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -ruthenium cmpds or catalyst [PLATINUM-GROUP METALS, COMPOUNDS] (Vol 19) -use of coordination compounds [COORDINATION COMPOUNDS] (Vol 7)... 

You saw in the last section that the preparation of allylic sulfides by displacement of, say, a halide from an allylic system is likely to give the more stable allylic sulfide whichever allylic halide is used and that the corresponding allylic sulfoxides are made by oxidation of the sulfide. The same is true of phosphorus compounds 73 used in chapter 15 to make dienes of fixed configuration. If R = OR, 73 is an allylic phosphonate for the Horner-Wadsworth-Emmons reaction but if R = Ph, 73 is a phosphine oxide for the Wittig-Horner reaction. 

A wide variety of photochemical transformations have been reported in organo-phosphorus compounds. Racemlzation of 1-phosphaallene enantiomers has been observed on exposure to light.Allyl diphenyl phosphate (211) undergoes a type II... 

The autoxidation of triphenylphosphine and phosphorus esters has been studied kinetically. After a short induction period the reaction gave the corresponding quinquecovalent phosphorus compounds. The intermediate (55) is probably formed by the addition of oxygen to perfluoroacyl-diarylphosphines. Subsequent decomposition afforded diarylphosphinates (56). The oxadiazine (57) has been prepared from the reaction of carbon dioxide and allyl isocyanate in the presence of tributylphosphine. ... 

Alkenes 1,4-dienes. Methylcopper induces the cross-coupling of dialkenyl-chloroboranes (5, 465-466) wilh allyl halides to form 1,4-dienes (equation 1). Coupling with an alkyl halide requires the presence of a phosphorus compound. 

Carbon-phosphorus bonds are formed by the Pd-catlyzed allylation of various phosphorus compounds (Scheme 13). The reaction of l-acetoxy-2-cyclohexene with LiPPh2 in refluxing THF provides an allylic phosphine in low yield (<15%). The phosphine produced deactivates the catalyst by coordination, which lowers the yield. In contrast, the reaction of LiP(S)Ph2 with l-acetoxy-2-cyclohexene takes place at room temperature to give allylic diphenylphosphine sulfides in 85% yield. ° Pd-catalyzed Michaelis-Arbuzov reaction of cinnamyl acetate with trimethyl phosphite affords a dimethyl allylic phospho-nate. With the reaction conditions being rather severe, this method may not be applicable to an allylic acetate that can produce a conjugated diene via /3-hydride elimination from the intermediate 7r-allylpalladium complex. 

Oxidation of Alcohols, Sulfur, and Phosphorus Compounds as well as Si-Si and Si-H Bonds. Bis(trimethylsilyl) peroxide acts as an effective oxidant for alcohols in the presence of p3tri-dinium dichromate or RuCLlPPhsls complex as the catalyst in CH2CI2. By this method, primary allylic and benzylic alcohols can be selectively oxidized to a-enals in the presence of a secondary alcohol. 

The title compounds also undergo the Claisen rarrangement (5-allyloxypyrazoles 4-allyl-5-pyrazolones) and are readily transformed into 5-chloropyrazoles by means of phosphorus oxychloride (8OCHE1). In the presence of aluminum chloride 5-acyloxypyrazoles (481) undergo the Fries rearrangement affording 4-acyl-5-hydroxypyrazoles (482). 

The title compound is formed by reaction of allyl alcohol with phosphorus trichloride and is reported to polymerise explosively if the material, when being purified by distillation, is taken down to less than half its bulk. 

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