A Rearrangement to Form Diethyl 1-Cyanoethyl Phosphate

Hall, Luther A. R.; Stephens, C. Wayne; Drysdale, J. J.

doi:10.1021/ja01564a071

Cited by 33 publications

(3 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The rearrangement of α-hydroxyphosphonates 1 to benzyl phosphates was first discovered through the example of the widely known insecticide prodrug, trichlorofon ( O , O -dimethyl (2,2,2-trichloro-1-hydroxyethyl)phosphonate) that is rearranged to 2,2-dichlorovinyl dimethyl phosphate (DDVP) acting as an acetylcholinesterase inhibitor [ 136 ]. Phosphonate-phosphate rearrangements were investigated in the presence of strong bases, such as sodium hydroxide [ 136 ], sodium ethoxide [ 137 ] and sodium hydride [ 138 ]. A number of protocols operated with triethylamine as the catalyst [ 139 , 140 , 141 ].…”

Section: Reactions Of α-Hydroxyphosphonatesmentioning

confidence: 99%

Synthesis and Reactions of α-Hydroxyphosphonates

Rádai

Keglevich

2018

Molecules

View full text Add to dashboard Cite

This review summarizes the main synthetic routes towards α-hydroxyphosphonates that are known as enzyme inhibitors, herbicides and antioxidants, moreover, a number of representatives express antibacterial or antifungal effect. Special attention is devoted to green chemical aspects. α-Hydroxyphosphonates are also versatile intermediates for other valuable derivatives. O-Alkylation and O-acylation are typical reactions to afford α-alkoxy-, or α-acyloxyphosphonates, respectively. The oxidation of hydroxyphosphonates leads to ketophosphonates. The hydroxy function at the α carbon atom of hydroxyphosphonates may be replaced by a halogen atom. α-Aminophosphonates formed in the nucleophilic substitution reaction of α-hydroxyphosphonates with primary or secondary amines are also potentially bioactive compounds. Another typical reaction is the base-catalyzed rearrangement of α-hydroxy-phosphonates to phosphates. Hydrolysis of the ester function of hydroxyphosphonates leads to the corresponding phosphonic acids.

show abstract

Section: Reactions Of α-Hydroxyphosphonatesmentioning

confidence: 99%

Synthesis and Reactions of α-Hydroxyphosphonates

Rádai

Keglevich

2018

Molecules

View full text Add to dashboard Cite

show abstract

“…Subsequently, other α-hydroxyphosphonates, not having a leaving group like chloride at the β-carbon atom, but an electron-withdrawing group on the α-carbon atom were shown to undergo the same transformation. [ 3 , 4 ] Therefore, a general reaction mechanism was proposed, which was later on proven by isotope labelling experiments (Scheme 2 ). [ 5 ]…”

Section: Introductionmentioning

confidence: 99%

The Stereochemical Course of the α‐Hydroxyphosphonate–Phosphate Rearrangement

Pallitsch

Roller

Hammerschmidt

2015

Chemistry A European J

View full text Add to dashboard Cite

The phosphonate–phosphate rearrangement is an isomerisation of α-hydroxyphosphonates bearing electron-withdrawing substituents at the α-carbon atom. We studied the stereochemical course of this rearrangement with respect to phosphorus. A set of four diastereomeric α-hydroxyphosphonates was prepared by a Pudovik reaction from two diastereomeric cyclic phosphites. The hydroxyphosphonates were separated and rearranged with Et3N as base. In analogy to trichlorphon, which was the first reported compound undergoing this rearrangement. All four hydroxyphosphonates could be rearranged to 2,2-dichlorovinyl phosphates. Single-crystal X-ray structure analyses of the α-hydroxyphosphonates and the corresponding phosphates allowed us to show that the rearrangement proceeds with retention of configuration on the phosphorus atom.

show abstract

“…In this context, [1,2]-Brook rearrangements involving the formal umpolung through silyl migration have been established as a powerful class of synthetic transformations . The analogous isoelectronic [1,2]-phosphonate–phosphate rearrangement, popularly recognized as a [1,2]-phospha-Brook rearrangement, has been embraced as a valuable synthetic tool in the modern era for transforming compounds containing carbonyl functionality into versatile carbanionic intermediates, which can potentially react with other classes of electrophiles and, hence, help in achieving chemical diversification. Typically, this molecular rearrangement proceeds through the formation of alkoxide ions by deprotonation of α-hydroxyphosphonates or the addition of a phosphite diester to carbonyl compounds and subsequent C → O phosphoryl migration under alkaline conditions generating α-oxygenated carbanions.…”

mentioning

confidence: 99%

Stereoselective Reductive Coupling Reactions Utilizing [1,2]-Phospha-Brook Rearrangement: A Powerful Umpolung Approach

Kaur

Singh

2023

J. Org. Chem.

View full text Add to dashboard Cite

Brook rearrangement entails the generation of α-oxygenated carbanions via the umpolung process. Recently, these anionic species have been widely utilized for several C−C bond forming strategies, providing various useful frameworks that are difficult to access through conventional approaches. However, the application of this powerful methodology in the development of chiral strategies is still at the nascent stage due to challenges involved in controlling chemoselectivity and enantioselectivity. This synopsis provides a detailed summary of diastereo-and/or enantioselective chemical transformations using [1,2]-phospha-Brook rearrangement.

show abstract

A Rearrangement to Form Diethyl 1-Cyanoethyl Phosphate

Cited by 33 publications

References 0 publications

Synthesis and Reactions of α-Hydroxyphosphonates

Synthesis and Reactions of α-Hydroxyphosphonates

The Stereochemical Course of the α‐Hydroxyphosphonate–Phosphate Rearrangement

Stereoselective Reductive Coupling Reactions Utilizing [1,2]-Phospha-Brook Rearrangement: A Powerful Umpolung Approach

Contact Info

Product

Resources

About