Expedient Synthesis of Substituted (Diphenylphosphinoylmethyl)benzenes

Bew, Sean P.; Brimage, Rebecca A.; Hughes, David L.; Legentil, Laurent; Sharma, Sunil V.; Wilson, Martin A.

doi:10.1021/jo062114k

“…Conventionally, heating arenecarboxylic acids, Ph 2 PCl (3 equiv), and water (2 equiv) at a high reaction temperature (180 °C) for a long time (100 h) produced the corresponding benzyl phosphoryl compounds. 19 Microwave irradiation improved the reaction to some extent; 20 however, the method still did not find application in organic synthesis due to the harsh reaction conditions. In 2020, Yamaguchi and co-workers described the deoxygenative phosphorylation of aromatic esters by P(O)-H compounds forming benzylic phosphoryl compounds through palladium catalysis (Scheme 5).…”

Section: Scheme 3 Cu-catalyzed and Aldehyde-induced Tandem Decarboxylmentioning

confidence: 99%

Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

Chen

¹

,

Tan

²

,

Liu

³

et al. 2020

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Herein, we highlight advances in the phosphorylation of readily available carboxylic acids and their derivatives forming synthetically important P(O)–sp3C, P(O)–sp2C, and P(O)–spC bonds, with an emphasis on the results demonstrated since 2010. This review examines the challenges associated with the use of this strategy for the synthesis of organophosphorus compounds and details advances in the design of catalytic systems that suppress these problems thus resulting in notable progress. Mechanistic details are discussed where available.1 Introduction2 Formation of P(O)–sp3C Bonds3 Formation of P(O)–sp2C Bonds4 Formation of P(O)–spC Bonds5 Outlook and Conclusion

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“…With the same Ph 2 PCl, Ishibashi showed that the reductive phosphorylation of trifluoroacetic acid (TFA) was successful and the reaction time could be dramatically shortened when the mixture was prestirred (80 h vs. 2.5 h) (Scheme 18 A, left) [137] . Capitalizing on microwave irradiation, Bew and his group slightly extended the scope to aromatic carboxylic acids, which gave several synthetically useful (diphenylphosphinoylmethyl)benzenes in moderate yields (Scheme 18 A, right) [138] …”

Section: Deoxygenative Functionalizations Of Carboxylic Acidsmentioning

confidence: 99%

Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids

Li

¹

,

Li

²

,

Huang

³

2022

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The simple and efficient conversion of carbonyl compounds into functionalized alkanes via deoxygenation is highly enabling in chemical synthesis. This Review covers the recent methodology development in carbonyl and carboxyl deoxygenative functionalizations, highlighting some representative and significant contributions in this field. These advances are categorized based on the reactivity patterns of some oxygenated feedstock compounds, including aldehydes, ketones and carboxylic acids. Four types of reactive intermediates arising from aldehydes and ketones during the deoxygenation, namely, bis‐electrophiles, carbenoids, bis‐nucleophiles and alkyl radical equivalents, are presented, while the carboxylic acids mainly behave as tris‐electrophiles when deoxygenated. In each subcategory, selected examples are organized according to the type of bond formation and discussed from a generalized mechanistic perspective.

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“…[137] Capitalizing on microwave irradiation, Bew and his group slightly extended the scope to aromatic carboxylic acids, which gave several synthetically useful (diphenylphosphinoylmethyl)benzenes in moderate yields (Scheme 18 A, right). [138] In 2020, Yamaguchi disclosed ag eneral deoxygenative phosphorylation method by means of palladium catalysis (Scheme 18 B). [139] When the notoriously reactive Ph 2 PCl was replaced with disubstituted phosphine oxide and sodium formate (HCO 2 Na), abroad range of benzylated phosphorus compounds could be obtained from free acids (18.1 and 18.2) or premade phenyl esters (18.3 to 18.5).…”

Section: Noncatalytic Reductive Amination Of Carboxylic Acidsmentioning

confidence: 99%

Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids

Li

¹

,

Huang

²

,

Li

³

2022

View full text Add to dashboard Cite

The simple and efficient conversion of carbonyl compounds into functionalized alkanes via deoxygenation is highly enabling in chemical synthesis. This Review covers the recent methodology development in carbonyl and carboxyl deoxygenative functionalizations, highlighting some representative and significant contributions in this field. These advances are categorized based on the reactivity patterns of some oxygenated feedstock compounds, including aldehydes, ketones and carboxylic acids. Four types of reactive intermediates arising from aldehydes and ketones during the deoxygenation, namely, bis‐electrophiles, carbenoids, bis‐nucleophiles and alkyl radical equivalents, are presented, while the carboxylic acids mainly behave as tris‐electrophiles when deoxygenated. In each subcategory, selected examples are organized according to the type of bond formation and discussed from a generalized mechanistic perspective.

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Expedient Synthesis of Substituted (Diphenylphosphinoylmethyl)benzenes

Cited by 4 publications

References 12 publications

Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

Phosphorylation of Carboxylic Acids and Their Derivatives with P(O)–H Compounds Forming P(O)–C Bonds

Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids

Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids

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