5186-73-2

Upstream product

• 644-97-3 Dichlorophenylphosphine 
• 106-99-0 buta-1,3-diene 
• 100-58-3 phenylmagnesium bromide 
• 822-47-9 1-Chloro-3-phospholene 1-oxide 
• 2501-98-6 diallyl(phenyl)phosphine oxide 
• 39063-70-2 1-oxo-1-hydroxyphospholene, β, γ-isomer 
• 824-72-6 P,P-dichlorophenylphosphine oxide 

Downstream Products

• 4963-91-1 1-phenylphospholane-1-oxide 
• 29618-43-7 3a,6b-dichloro-5ξ-oxo-5ξ-phenyl-(3ar,3bc,6ac,6bc)-hexahydro-5λ⁵-phospholo[3',4':3,4]cyclobuta[1,2-c]pyrrole-1,3-dione 
• 56562-96-0 2,4,9-triphenyl-2,3-dihydro-1H-[1,3,2]diazaphosphonine 2-oxide 
• 49595-39-3 2,7-diphenyl-2,3-dihydro-1H-[1,2]azaphosphepine 2-oxide 
• 56562-97-1 2-phenyl-4,9-bis-(3,4,5-trimethoxy-phenyl)-2,3-dihydro-1H-[1,3,2]diazaphosphonine 2-oxide 
• 28278-54-8 1-phenyl-2,3-dihydro-1H-phosphole 
• 20380-19-2 3,4-Dibromophospholane oxide 
• 125344-77-6 4-Bromo-1-phenyl-2-phospholene 1-oxide 
• 72811-99-5 3-chloro-4-hydroxy-1-phenyl-1-oxo-phospholane 
• 119280-21-6 t-3-bromo-r-4-hydroxy-1-phenylphospholane-1-oxide 
• 85281-93-2 trans-3,4-epoxy-1-phenylphospholane-1-oxide 
• 91597-48-7 c-3,c-4-dihydroxy-1-phenylphospholane-1-oxide 
• 91685-13-1 t-3,t-4-dihydroxy-1-phenylphospholane-1-oxide 

Relevant academic research and scientific papers

Preparation method of phospholene oxide, substituted phospholene oxide and preparation method of substituted phospholene oxide

The invention relates to a preparation method of phospholene oxide, substituted phospholene oxide and a preparation method of the substituted phospholene oxide and belongs to the technical field of organic synthesis. The preparation method of the phospholene oxide comprises the following steps: 1) enabling phosphorus trihalide and chloroethanol to react at -10 to 40 DEG C for 0.5 to 3h so as to obtain a compound shown as a formula I; 2) enabling the compound shown as the formula I, a catalyst, a polymerization inhibitor and 1,3-butadiene to react at room temperature for 4 to 10h; then raisingthe temperature to 40 to 80 DEG C and reacting for 12 to 24h; then raising the temperature to 80 to 100 DEG C and reacting for 8 to 14h to obtain the phospholene oxide. The e preparation method of thephospholene oxide, provided by the invention, takes the phosphorus halide and the chloroethanol as raw materials, and the raw materials are easy to obtain and the price is low; reaction conditions are moderate and the method is simple and feasible and is low-cost.

Dynamic Kinetic Resolution in Rhodium-Catalyzed Asymmetric Arylation of Phospholene Oxides

The reaction of 2,5-dihydro-1H-phosphole 1-oxide 1 with ArB(pin) 3 in the presence of a chiral (R)-segphos-rhodium catalyst under highly basic conditions (10 equiv of KOH) gave high yields of (1S,3S)-3-arylphospholane 1-oxide 4 with high diastereoselectivity as well as high enantioselectivity. Equilibration of 1 with its 2,3-dihydro isomer 2, which is chiral and racemic, by base-catalyzed olefin isomerization followed by kinetic resolution of 2 with the chiral rhodium catalyst realized the present dynamic kinetic resolution.

METHODS FOR PHOSPHINE OXIDE REDUCTION IN CATALYTIC WITTIG REACTIONS

A method for increasing the rate of phosphine oxide reduction, preferably during a Wittig reaction comprising use of an acid additive is provided. A room temperature catalytic Wittig reaction (CWR) the rate of reduction of the phosphine oxide is increased due to the addition of the acid additive is described. Furthermore, the extension of the CWR to semi-stabilized and non-stabilized ylides has been accomplished by utilization of a masked base and/or ylide-tuning.

Catalytic wittig reactions of semi- and nonstabilized ylides enabled by ylide tuning

The first examples of catalytic Wittig reactions with semistabilized and nonstabilized ylides are reported. These reactions were enabled by utilization of a masked base, sodium tert-butyl carbonate, and/or ylide tuning. The acidity of the ylide-forming proton was tuned by varying the electron density at the phosphorus center in the precatalyst, thus facilitating the use of relatively mild bases. Steric modification of the precatalyst structure resulted in significant enhancement of E selectivity up to >95:5, E/Z. Time for a tune up: Catalytic Wittig reactions with semi- and nonstabilized ylides were enabled by use of a masked base (NaOCO2tBu) and/or ylide tuning. The acidity of the ylide-forming proton was tuned by varying the electron density at the P center in the precatalyst, thus facilitating the use of relatively mild bases. Steric modification of the precatalyst structure resulted in significant enhancement of E selectivity.

Breaking the ring through a room temperature catalytic wittig reaction

One ring no longer rules them all: Employment of 2.5-10 mol % of 4-nitrobenzoic acid with phenylsilane led to the development of a room temperature catalytic Wittig reaction (see scheme). Moreover, these enhanced reduction conditions also facilitated the use of acyclic phosphine oxides as catalysts for the first time. A series of alkenes were produced in moderate to high yield and selectivity. Copyright

Part I: The development of the catalytic wittig reaction

We have developed the first catalytic (in phosphane) Wittig reaction (CWR). The utilization of an organosilane was pivotal for success as it allowed for the chemoselective reduction of a phosphane oxide. Protocol optimization evaluated the phosphane oxide precatalyst structure, loading, organosilane, temperature, solvent, and base. These studies demonstrated that to maintain viable catalytic performance it was necessary to employ cyclic phosphane oxide precatalysts of type 1. Initial substrate studies utilized sodium carbonate as a base, and further experimentation identified N,N-diisopropylethylamine (DIPEA) as a soluble alternative. The use of DIPEA improved the ease of use, broadened the substrate scope, and decreased the precatalyst loading. The optimized protocols were compatible with alkyl, aryl, and heterocyclic (furyl, indolyl, pyridyl, pyrrolyl, and thienyl) aldehydes to produce both di- and trisubstituted olefins in moderate-to-high yields (60-96 %) by using a precatalyst loading of 4-10 mol %. Kinetic E/Z selectivity was generally 66:34; complete E selectivity for disubstituted α,β-unsaturated products was achieved through a phosphane-mediated isomerization event. The CWR was applied to the synthesis of 54, a known precursor to the anti-Alzheimer drug donepezil hydrochloride, on a multigram scale (12.2 g, 74 % yield). In addition, to our knowledge, the described CWR is the only transition-/heavy-metal-free catalytic olefination process, excluding proton-catalyzed elimination reactions. A point of difference: By utilizing an organosilane to chemoselectively reduce a phosphane oxide precatalyst to a phosphane (see scheme), the first catalytic (in phosphane) Wittig reaction has been developed. The methodology has been applied to the synthesis of 22 disubstituted and 24 trisubstituted olefins, including a multigram synthesis of a precursor to the anti-Alzheimer drug donepezil hydrochloride.

A novel access to alicyclic phosphine oxides via ring closing metathesis

A series of cyclic phosphine oxides 5a-e was prepared in a one-step procedure by RCM of dienes 4a-e. The methodology was extended to the preparation of the bis-phosphine oxide 5f.

Phospho Sugars; Novel Preparation and Their Glycosyl Compounds

Treatment of 1-phenyl-2-, and -3-phospholene 1-oxides with N-bromosuccinimide affords 4-bromo-1-phenyl-2-phospholene 1-oxide.Substitution of the bromide with acetate, followed by stereoselective oxidation with osmium tetroxide and peracetylation with acetic anhydride/pyridine affords phospho sugar derivatives of tetrafuranose.Furthermore, N-, O-, and S-glycosyl compounds of phospho sugars can be prepared from 3-methyl-1-phenyl-2-phospholene 1-oxide by bromination and nucleophilic substitution reactions.This is a novel and excellent route to prepare phospho sugar derivatives.