1779-58-4

Usage

Uses

Used in Pharmaceutical Industry:
(Carbomethoxymethyl)triphenylphosphonium bromide is used as a reactant for the synthesis of GSK-3 inhibitors, which are crucial in the development of drugs targeting various diseases, including neurodegenerative and metabolic disorders.
Used in Antifungal and Cytostatic Applications:
In the field of antifungal and cytostatic applications, (Carbomethoxymethyl)triphenylphosphonium bromide serves as a reactant for the synthesis of substituted furanones. These compounds exhibit significant antifungal and cytostatic activities, making them valuable in the development of new treatments for fungal infections and cancer.
Used in Photochromic Applications:
(Carbomethoxymethyl)triphenylphosphonium bromide is used as a reactant in the synthesis of photochromic dithienylethene derivatives. These derivatives are essential in the development of advanced materials for optical data storage, smart windows, and other applications that require reversible photochromic properties.
Used in Organic Synthesis:
The compound is also used as a reactant for the synthesis of gem-diiodoalkanes containing allylic alcohols. This application is significant in organic synthesis, as these gem-diiodoalkanes are valuable intermediates for the preparation of various complex organic molecules.
Used in the Synthesis of Highly Substituted Cyclopentenes:
(Carbomethoxymethyl)triphenylphosphonium bromide is utilized in the synthesis of highly substituted cyclopentenes through Au-catalyzed deoxygenative Nazarov cyclization. These cyclopentenes are important building blocks in the creation of natural products and pharmaceutical compounds.
Used in Asymmetric Hydrogenation:
In the field of asymmetric hydrogenation, (Carbomethoxymethyl)triphenylphosphonium bromide is used as a reactant for the asymmetric hydrogenation of α,β-unsaturated ester-phosphonates. This process is crucial in the synthesis of enantiomerically pure compounds, which are essential in the pharmaceutical industry for the development of chiral drugs.
Used in Studies of Thermal Decomposition:
Lastly, (Carbomethoxymethyl)triphenylphosphonium bromide is used in the study of the thermal decomposition of phosphonium alkyl ester salts. Understanding the decomposition behavior of these salts is vital for optimizing reaction conditions and improving the overall efficiency of synthetic processes.

Purification Methods

Wash it with pet ether (b 40-50o), recrystallise it from CHCl3/Et2O and dry it at high vacuum at 65o. [Isler et al. Helv Chim Acta 40 1242 1957, Wittig & Haag Chem Ber 88 1654, 1664 1955, Beilstein 16 IV 981.]

InChI:InChI=1/C21H20O2P.BrH/c1-23-21(22)17-24(18-11-5-2-6-12-18,19-13-7-3-8-14-19)20-15-9-4-10-16-20;/h2-16H,17H2,1H3;1H/q+1;/p-1

Upstream product

• 96-32-2 bromoacetic acid methyl ester 
• 603-35-0 triphenylphosphine 
• 21204-67-1 methyl (triphenylphosphoranylidene)acetate 
• 134898-25-2 (2-Benzoyl-2-bromo-1-methoxycarbonyl-3-oxo-3-phenyl-propyl)-triphenyl-phosphonium; bromide 
• 134898-34-3 [(2-Bromo-1,3-dioxo-indan-2-yl)-methoxycarbonyl-methyl]-triphenyl-phosphonium; bromide 
• 1685-97-8 2,2-dibromo-indan-1,3-dione 
• 16619-55-9 3,3-dibromo-1,3-diphenyl-1,3-propanedione 

Downstream Products

• 21204-67-1 methyl (triphenylphosphoranylidene)acetate 
• 120626-55-3 3-phenyl-5-[(E)-(methoxycarbonylmethylidene)]-2-furanone 
• 116998-18-6 4-Chloro-4,4-difluoro-3-oxo-2-(triphenyl-λ⁵-phosphanylidene)-butyric acid methyl ester 
• 53780-99-7 2',4'-diphenyl-dispiro[anthracene-9,1'-cyclobutan-3',9''-anthracene]-10,10''-dione 
• 603-35-0 triphenylphosphine 
• 1664-59-1 3-(3-nitrophenyl)acrylic acid methyl ester 
• 97055-33-9 methyl 3-(dichloromethyl)-4,4-dichlorocrotonate 
• 921-03-9 1,1,3-trichloroacetone 
• 203861-32-9 4-(6-benzyloxy-2,5,7,8-tetramethylchroman-2-yl)but-3-en-2-one 
• 193151-10-9 3-(3-cyano-phenyl)-acrylic acid methyl ester 
• 405551-66-8 (E)-3-(4-Chloro-phenyl)-3-pyridin-2-yl-acrylic acid methyl ester 
• 58336-35-9 coumarin-6H 
• 111171-94-9 3-(m-methylphenyl)-1-propanol 
• 22991-03-3 3-(3-chlorophenyl)propanol 

Relevant academic research and scientific papers

Cicindeloine from Stenus cicindeloides-isolation, structure elucidation, and total synthesis

The new piperideine alkaloid cicindeloine (3) was isolated from the pygidial glands of the beetles Stenus cicindeloides and Stenus solutus. The structure and absolute configuration of 3 were elucidated by NMR spectroscopy and asymmetric synthesis, respect

Tandem Conjugate addition of Silylcuprate and Benzenesulfenyl Chloride to Unsaturated Esters: Stereoselective Preparation of anti-3-Dimethylphenylsilyl-2-phenylthio Aldehydes

Conjugate addition of dimethylphenylsilylcuprate is successful even to a 2,3-disubstituted acrylate ester and when followed by α-sulfenylation of the trapped silyl enol ether intermediate, reduction and re-oxidation gives, for example, (2SR,3RS)-(anti)-2,

Synthesis of lignin model compound containing a β-O-4 linkage

Development of catalysts for efficient conversion of lignin polymer to value-added materials requires appropriately-functionalized lignin model compounds. The predominant structural feature of lignin biopolymer is an extensive network of β-O-4 linkages. A

Organocatalyzed [2+2] Cycloaddition Reactions between Quinone Imine Ketals and Allenoates

A new cycloaddition reaction of quinone imine ketals (QIKs), which could be utilized to the construction of functionalized azaspirocyclics under mild conditions, is described. This transformation involved a [2+2] cycloaddition reaction between QIKs and allenoates catalyzed by DABCO, and then treatment with 1 N HCl in one-pot. The strategy could provide a practical route to access azetidine-fused spirohexadienones in good to excellent yields and with high E -selectivity.

Catalytic asymmetric [3+2] cycloaddition of isomünchnones with methyleneindolinones

An efficient enantioselective [3+2] cycloaddition of isomünchnones with methyleneindolinones that are generated by anin situintramolecular addition of the carbonyl group to rhodium carbenes is realized with a chiralN,N′-dioxide/Zn(ii) complex as a Lewis acid. A series of chiral oxa-bridged 3-spiropiperidines are obtained in high yields with excellent dr and excellent ee values.

Substituted dienes prepared from betulinic acid – Synthesis, cytotoxicity, mechanism of action, and pharmacological parameters

A set of new substituted dienes were synthesized from betulinic acid by its oxidation to 30-oxobetulinic acid followed by the Wittig reaction. Cytotoxicity of all compounds was tested in vitro in eight cancer cell lines and two noncancer fibroblasts. Almost all dienes were more cytotoxic than betulinic acid. Compounds 4.22, 4.30, 4.33, 4.39 had IC50 below 5 μmol/L; 4.22 and 4.39 were selected for studies of the mechanism of action. Cell cycle analysis revealed an increase in the number of apoptotic cells at 5 × IC50 concentration, where activation of irreversible changes leading to cell death can be expected. Both 4.22 and 4.39 led to the accumulation of cells in the G0/G1 phase with partial inhibition of DNA/RNA synthesis at 1 × IC50 and almost complete inhibition at 5 × IC50. Interestingly, compound 4.39 at 5 × IC50 caused the accumulation of cells in the S phase. Higher concentrations of tested drugs probably inhibit more off-targets than lower concentrations. Mechanisms disrupting cellular metabolism can induce the accumulation of cells in the S phase. Both compounds 4.22 and 4.39 trigger selective apoptosis in cancer cells via intrinsic pathway, which we have demonstrated by changes in the expression of the crucial apoptosis-related protein. Pharmacological parameters of derivative 4.22 were superior to 4.39, therefore 4.22 was the finally selected candidate for the development of anticancer drug.

Enantioselective Rauhut–Currier Reaction with β-Substituted Acrylamides Catalyzed by N-Heterocyclic Carbenes

β-Substituted acrylamides have low electrophilicity and are yet to be exploited in the enantioselective Rauhut–Currier reaction. By exploiting electron-withdrawing protection of the amide and moderate nucleophilicity N-heterocyclic carbenes, such substrates have been converted to enantioenriched quinolones. The reaction proceeds with complete diastereoselectivity, good yield, and modest enantioselectivity. Derivatizations are reported, as are computational studies, supporting decreased amide bond character with electron-withdrawing protection of the nitrogen.

Enantioselective Allenoate-Claisen Rearrangement Using Chiral Phosphate Catalysts

Herein we report the first highly enantioselective allenoate-Claisen rearrangement using doubly axially chiral phosphate sodium salts as catalysts. This synthetic method provides access to β-amino acid derivatives with vicinal stereocenters in up to 95percent ee. We also investigated the mechanism of enantioinduction by transition state (TS) computations with DFT as well as statistical modeling of the relationship between selectivity and the molecular features of both the catalyst and substrate. The mutual interactions of charge-separated regions in both the zwitterionic intermediate generated by reaction of an amine to the allenoate and the Na+-salt of the chiral phosphate leads to an orientation of the TS in the catalytic pocket that maximizes favorable noncovalent interactions. Crucial arene-arene interactions at the periphery of the catalyst lead to a differentiation of the TS diastereomers. These interactions were interrogated using DFT calculations and validated through statistical modeling of parameters describing noncovalent interactions.

Phosphine-catalyzed dearomative [3+2] annulation of 3-nitroindoles and allenoates

The efficient phosphine-catalyzed dearomative [3+2] annulation of 3-nitroindoles with allenoates has been successfully developed, providing a facile access to cyclopenta[b]indolines with good to excellent yields and high diastereoselectivities. This strategy features mild reaction conditions, high functional group tolerance, and scalability. Additionally, the 2-nitrobenzofuran and 2-nitrobenzothiophene were good dearomative [3+2] annulation partners.

Intermolecular Dehydrative Coupling and Intramolecular Cyclization of Ruthenium Vinylidene Complexes Formed from Aromatic Propynes Containing Carbonyl Functionalities

A remarkable intermolecular dehydrative coupling reaction with the formation of a C?C bond was found for the vinylidene complex 2 a, yielding the dinuclear bisvinylidene complex 4 a. Complex 2 a containing 1-hydroxyindan moiety was first formed from the reaction of o-propynyl benzaldehyde 1 a with [Ru]–Cl ([Ru]=Cp(PPh3)2Ru) by a cyclization process. For analogous aldehyde 1 b containing an additional 1,3-dioxolane group on the aryl ring, similar intermolecular coupling yields the dinuclear bisvinylidene complex 4 b. However, the fluoro group on the aryl ring in aldehyde 1 c inhibits the coupling reaction, giving only the vinylidene complex 2 c. For the reactions of [Ru]–Cl in MeOH with compounds 1 f, 1 g and 1 h, each with a ketone functionality, cyclization gives vinylidene complexes 2 f, 2 g and 2 h, respectively. However, no similar intermolecular coupling was observed, instead, the intramolecular dehydration yields 8 f, 8 g and 8 h, respectively. In CDCl3, catalytic cyclization is observed for the o-propynylphenyl ketone 1 h with [Ru]–Cl at 50 °C giving the isochromene products 14 h. Furthermore, treatment of the o-propynylaryl α,β-unsaturated ketones 1 k–m and 1 n with [Ru]–Cl in MeOH affords the corresponding vinylidene complexes 10 k–m and 11 n each with 1-benzosuberone moiety in the presence of NH4PF6. These intramolecular cyclization products were formed by the addition of Cβ onto the terminal carbon of the alkene moiety. All these reaction products were characterized by spectroscopic methods. In addition, structures of complexes 4 a, and 10 l were confirmed by single crystal X-ray diffraction analysis.