The conversion of ether bonds to hydroxyl <i>via</i> a base-promoted rearrangement of cyclic phosphine oxides

Li, Zhancai; Yan, Bing-Xia; Wang, Xiaoning; Zhai, De-Hua; Li, Qiang; Zheng, Hang; Zhao, Chang‐Qiu

doi:10.1039/d1qo00925g

N‐Heterocyclic Carbene Enabled Copper Catalyzed Asymmetric Synthesis of Pyrimidinyl Phosphine with both Axial and P‐Stereogenicity

Cui,

Zhang,

Huang

et al. 2024

Angewandte Chemie

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P‐stereogenic phosphines, renowned for their utility as ligands and catalysts, have been instrumental in the field of asymmetric catalysis. However, the catalytic asymmetric synthesis of chiral ligands possessing both axial and phosphine chirality remains a significant challenge. Here, we present the successful demonstration of a Cu‐catalyzed asymmetric C‐P construction using in situ generated secondary phosphine and heteroaryl chloride. By introducing a chiral NHC ligand and an achiral diphosphine auxiliary ligand, we effectively alleviated the poisoning effect caused by phosphine(III) compounds and suppressed the nonenantioselective background reaction. The reaction exhibited excellent enantioselectivity, with up to 96% ee, and good diastereoselectivity, with up to 14:1 dr, when employing less sterically hindered secondary phosphines. This particular substrate poses a significant challenge due to its strong poisoning effect in copper catalysis.

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N‐Heterocyclic Carbene Enabled Copper Catalyzed Asymmetric Synthesis of Pyrimidinyl Phosphine with both Axial and P‐Stereogenicity

Cui,

Zhang,

Huang

et al. 2024

Angew Chem Int Ed

0

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P‐stereogenic phosphines, renowned for their utility as ligands and catalysts, have been instrumental in the field of asymmetric catalysis. However, the catalytic asymmetric synthesis of chiral ligands possessing both axial and phosphine chirality remains a significant challenge. Here, we present the successful demonstration of a Cu‐catalyzed asymmetric C‐P construction using in situ generated secondary phosphine and heteroaryl chloride. By introducing a chiral NHC ligand and an achiral diphosphine auxiliary ligand, we effectively alleviated the poisoning effect caused by phosphine(III) compounds and suppressed the nonenantioselective background reaction. The reaction exhibited excellent enantioselectivity, with up to 96% ee, and good diastereoselectivity, with up to 14:1 dr, when employing less sterically hindered secondary phosphines. This particular substrate poses a significant challenge due to its strong poisoning effect in copper catalysis.

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Advancement in Synthetic Strategies of Phosphorus Heterocycles: Recent Progress from Synthesis to Emerging Class of Optoelectronic Materials

Thakur,

Sushmita,

Meena

et al. 2024

The Chemical Record

1

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Organophosphorus heterocycles have long been acknowledged for their significant potential across diverse fields, including catalysis, material science, and drug development. Incorporating phosphorus functionalities into organic compounds offers a means to effectively tailor their medicinal properties, augment biological responses, and enhance selectivity and bioavailability. The distinctive physical and photoelectric characteristics of phosphorus‐containing conjugated compounds have garnered considerable interest as promising materials for organic optoelectronics. These compounds find extensive utility in various applications such as light‐emitting diodes, photovoltaic cells, phosphole‐based fluorophores, and semiconductors.

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The conversion of ether bonds to hydroxyl via a base-promoted rearrangement of cyclic phosphine oxides

Abstract: Biphenyl derived secondary phosphine oxides having 2’-hydroxyl were prepared. The compound were converted to hydroxymethyl phosphine oxides when reacted with formaldehyde. After chlorination and cyclization, a series of P,O-heterocycles were...

Cited by 5 publications

References 35 publications

N‐Heterocyclic Carbene Enabled Copper Catalyzed Asymmetric Synthesis of Pyrimidinyl Phosphine with both Axial and P‐Stereogenicity

N‐Heterocyclic Carbene Enabled Copper Catalyzed Asymmetric Synthesis of Pyrimidinyl Phosphine with both Axial and P‐Stereogenicity

N‐Heterocyclic Carbene Enabled Copper Catalyzed Asymmetric Synthesis of Pyrimidinyl Phosphine with both Axial and P‐Stereogenicity

Advancement in Synthetic Strategies of Phosphorus Heterocycles: Recent Progress from Synthesis to Emerging Class of Optoelectronic Materials

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