Primary phosphine chemistry

Fleming, James T.; Higham, Lee J.

doi:10.1016/j.ccr.2015.03.002

Cited by 49 publications

(56 citation statements)

References 107 publications

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“…These functional groups are ideal candidates for polymer synthesis because they are currently produced industrially, easily synthesized in the lab, and possess diverse reactivity. 21 Currently there is strong evidence that reactivity is retained in the air-stable varieties, including but not limited to macrocycle and phosphoramidate formation, 22,23 however this has not been determined for radical additions of P-H bonds to olefins. 15 This approach allows for the fabrication of materials possessing phosphine functionalities that exhibit a variety of functional applications, including oxygen scavenging and solid-supported chemistry.…”

Section: Introductionmentioning

confidence: 99%

Phosphane–ene chemistry: the reactivity of air-stable primary phosphines and their compatibility with the thiol–ene reaction

2015

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Air-sensitive and air-stable primary phosphines (RPH2) were compared for their ability to undergo photoinitiated phosphane-ene chemistry with 1-hexene. Despite their increased air-stability, the primary phosphines displayed equal to or greater reactivity when compared to air-sensitive alkyl or aryl analogues. The phosphane-ene reaction was also performed in the presence of 1-octanethiol to determine whether thiol-ene and phosphane-ene chemistries could proceed simultaneously. It was determined that the phosphane-ene process takes precedence over thiol-ene as P-H bond conversion was independent of thiol concentration. Tertiary phosphine (R3P) and some secondary phosphine (R2PH) products were found to react with thiols under experimental conditions to create phosphine-sulfides (P-S), but this chemistry only proceeded at low P-H bond concentrations. These results suggests that hydrogen transfer reactions take precedence over P-S formation and demonstrate the unique relationship between phosphane-ene and thiol-ene chemistry.

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Section: Introductionmentioning

confidence: 99%

Phosphane–ene chemistry: the reactivity of air-stable primary phosphines and their compatibility with the thiol–ene reaction

2015

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“…Primary phosphines can be difficult to handle due to toxicity and facile oxidation that renders many simple derivatives pyrophoric. A vigorous effort to understand and expend the family of airstable primary phosphines emerged in recent years to avail greater use of these molecules [12][13][14][15]. Among this class of primary phosphines are 8-[(4-phosphino)phenyl]-4,4-dimethyl-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene (2) [12,[15][16][17][18] and (2′-methoxy-[1,1′-binaphthalen]-2-yl)phosphine (3) [19,20] (Figure 1).…”

Section: Resultsmentioning

confidence: 99%

Zirconium-Catalyzed Alkene Hydrophosphination and Dehydrocoupling with an Air-Stable, Fluorescent Primary Phosphine

et al. 2016

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Zirconium-catalyzed alkene hydrophosphination and dehydrocoupling with an air-stable, fluorescent primary phosphine 8-[(4-phosphino)phenyl]-4,4-dimethyl-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene furnishes fluorescent phosphine products. Hydrophosphination of the fluorescent phosphine produces products with a complete selectivity for the secondary product. A key intermediate in catalysis, a zirconium phosphido compound, was isolated.

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“…The precise mechanism of oxidation of phosphines and their heterocycles in air remains elusive, with studies limited to discussions in regards to primary phosphine. [24][25][26][27] These have relied on photolytic oxidation experiments of tertiary phosphines and have indicated possible formation of a phosphine radical cation species that reacts with O 2 , resulting in a phosphine peroxy radical cation quenching with the addition of a second phosphine to generate two equivalents of phosphine oxide (Scheme 2). [28][29][30][31] If this mechanism was responsible for oxidation, then it is the radical cation species that is of interest as a key high-energy intermediate, with the ease of formation and reactivity of the radical cation also likely dictating the rate of oxidation for phosphiranes.…”

Section: Introductionmentioning

confidence: 99%

Predicting phosphirane air stability using density functional theory

Gaston

McCosker

et al. 2020

J of Physical Organic Chem

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Phosphorus 3‐membered heterocycles, phosphiranes, provide an interesting synthetic scaffold with a potentially diverse range of reactions that are currently underexplored. This is in part due to their difficulty in synthesis, with many products and intermediates containing low air stability. With the application and extension of a density functional theory (DFT) model to phosphiranes by calculation at the UB3LYP/6‐31G(d) level of their radical cation singly occupied molecular orbital (SOMO), a correlation between calculated and relative experimental air stability has been demonstrated. The model also accounts for the stability of many synthesised substituted and unsubstituted phosphiranes and has allowed new synthetic targets to be identified, in particular, 1‐(2,4,6‐tri‐tert‐butoxyphenyl)phosphirane exhibited high theoretical air stability. Because of the simplicity and efficiency of the model, its application enables phosphiranes to be screened for high bench stability, providing accessibility for their use in synthetic chemistry, in turn, realising the potential for incorporation of phosphiranes into complex synthetic strategies.

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Primary phosphine chemistry

Cited by 49 publications

References 107 publications

Phosphane–ene chemistry: the reactivity of air-stable primary phosphines and their compatibility with the thiol–ene reaction

Phosphane–ene chemistry: the reactivity of air-stable primary phosphines and their compatibility with the thiol–ene reaction

Zirconium-Catalyzed Alkene Hydrophosphination and Dehydrocoupling with an Air-Stable, Fluorescent Primary Phosphine

Predicting phosphirane air stability using density functional theory

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