Chemistry of 3-membered carbon-phosphorus heterocycles

Mathey, François

doi:10.1021/cr00104a004

Cited by 270 publications

(118 citation statements)

References 61 publications

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“…[14] The structural data of the C 2 P ring of 7 b compare well with those of W(CO) 5 -complexed phosphiranes. [15] For example, the PÀC bond lengths of 1.8053(18) and 1.8115(19) are in the normal range (1.78-1.89 ) as is the 50.52(9)8 CPC angle (47. 4-51.18).…”

Section: Resultsmentioning

confidence: 99%

Strained, Stable 2‐Aza‐1‐Phosphabicyclo[n.1.0]alkane and ‐alkene Fe(CO)₄ Complexes with Dynamic Phosphinidene Behavior

Borst

Riet

Lemmens

et al. 2005

Chemistry A European J

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The synthesis of highly strained bicyclic phosphirane and phosphirene iron–tetracarbonyl complexes, that is, complexes with 2‐aza‐1‐phosphabicyclo[n.1.0]alkanes and ‐alkenes (n=3–5), is explored by using intramolecular cycloaddition of an in situ generated electrophilic phosphinidene complex, [R(iPr)NPFe(CO)4], to its CC‐ and CC‐containing R substituent. Saturated bicyclic complexes 7 a–c with n=4–2 are remarkably stable, as illustrated by the X‐ray crystal structure for 7 b (n=3), yet all readily undergo retroaddition to react with phenylacetylene. Shuttling of the phosphinidene iron complex between two equivalent CC groups is demonstrated for a 1‐butene‐substituted 2‐aza‐1‐phosphabicyclo[3.1.0]hexane by selective 1H NMR magnetization transfer from the phosphirane protons to the olefinic protons. Even the more strained unsaturated bicycles 17 a,b (n=4,3) are surprisingly stable as illustrated by the X‐ray crystal structure for 17 a (n=4), but the smaller phosphabicyclo[3.1.0]hex‐5‐ene (17 c, n=2) dimerizes to tricyclic 19 with a unique ten‐membered heterocyclic ring; an X‐ray crystal structure is reported. Like their saturated analogues also the bicyclic phosphirenes readily undergo retroaddition as shown by the reaction of their phosphinidene iron moiety with phenylacetylene.

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Section: Resultsmentioning

confidence: 99%

Strained, Stable 2‐Aza‐1‐Phosphabicyclo[n.1.0]alkane and ‐alkene Fe(CO)₄ Complexes with Dynamic Phosphinidene Behavior

Borst

Riet

Lemmens

et al. 2005

Chemistry A European J

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“…The existence of stable 3-membered rings with P is well documented [51,52]. A possible nucleophilic reaction for the formation of these intermediates based on the attack by HO…”

Section: A C C E P T E D Accepted Manuscriptmentioning

confidence: 98%

Enhanced electro-oxidation resistance of carbon electrodes induced by phosphorus surface groups

Berenguer

Ruiz-Rosas

Gallardo

et al. 2015

Carbon

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ABSTRACT:The electro-oxidation of carbon materials enormously degrades their performance and limits their wider utilization in multiple electrochemical applications.In this work, the positive influence of phosphorus functionalities on the overall electrochemical stability of carbon materials has been demonstrated under different conditions. We show that the extent and selectivity of electroxidation in P-containing carbons are completely different to those observed in conventional carbons without P.The electro-oxidation of P-containing carbons involves the active participation of phosphorus surface groups, which are gradually transformed at high potentials from less-to more-oxidized species to slow down the introduction of oxygen groups on the carbon surface (oxidation) and the subsequent generation of (C*OOH)-like unstable promoters of electro-gasification. The highest-oxidized P groups (-C-O-P-like species) seem to distribute the gained oxygen to neighboring carbon sites, which finally suffer oxidation and/or gasification. So it is thought that P-groups could act as mediators of carbon oxidation although including various steps and intermediates compared to electroxidation in P-free materials.

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“…Several strategies for the preparation of P-heterocycles have been described over the last years, and excellent reviews have been published [90][91][92][93]. In the past 20 years, significant effort has been devoted to synthetic and reactivity studies of this particular class of compounds, here we only report the stereoselective methods recently reported in the literature where the α-amino-C-phosphinate motif is incorporated.…”

Section: Synthesis Of Phosphacyclic α-Amino-c-phosphinatesmentioning

confidence: 99%

Stereoselective Synthesis of α-Amino-C-phosphinic Acids and Derivatives

et al. 2016

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α-Amino-C-phosphinic acids and derivatives are an important group of compounds of synthetic and medicinal interest and particular attention has been dedicated to their stereoselective synthesis in recent years. Among these, phosphinic pseudopeptides have acquired pharmacological importance in influencing physiologic and pathologic processes, primarily acting as inhibitors for proteolytic enzymes where molecular stereochemistry has proven to be critical. This review summarizes the latest developments in the asymmetric synthesis of acyclic and phosphacyclic α-amino-C-phosphinic acids and derivatives, following in the first case an order according to the strategy used, whereas for cyclic compounds the nitrogen embedding in the heterocyclic core is considered. In addition selected examples of pharmacological implications of title compounds are also disclosed.

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Chemistry of 3-membered carbon-phosphorus heterocycles

Cited by 270 publications

References 61 publications

Strained, Stable 2‐Aza‐1‐Phosphabicyclo[n.1.0]alkane and ‐alkene Fe(CO)₄ Complexes with Dynamic Phosphinidene Behavior

Strained, Stable 2‐Aza‐1‐Phosphabicyclo[n.1.0]alkane and ‐alkene Fe(CO)₄ Complexes with Dynamic Phosphinidene Behavior

Enhanced electro-oxidation resistance of carbon electrodes induced by phosphorus surface groups

Stereoselective Synthesis of α-Amino-C-phosphinic Acids and Derivatives

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Chemistry of 3-membered carbon-phosphorus heterocycles

Cited by 270 publications

References 61 publications

Strained, Stable 2‐Aza‐1‐Phosphabicyclo[n.1.0]alkane and ‐alkene Fe(CO)4 Complexes with Dynamic Phosphinidene Behavior

Strained, Stable 2‐Aza‐1‐Phosphabicyclo[n.1.0]alkane and ‐alkene Fe(CO)4 Complexes with Dynamic Phosphinidene Behavior

Enhanced electro-oxidation resistance of carbon electrodes induced by phosphorus surface groups

Stereoselective Synthesis of α-Amino-C-phosphinic Acids and Derivatives

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Strained, Stable 2‐Aza‐1‐Phosphabicyclo[n.1.0]alkane and ‐alkene Fe(CO)₄ Complexes with Dynamic Phosphinidene Behavior

Strained, Stable 2‐Aza‐1‐Phosphabicyclo[n.1.0]alkane and ‐alkene Fe(CO)₄ Complexes with Dynamic Phosphinidene Behavior