The Synthesis, Crystal Structure, Modification, and Cytotoxic Activity of α-Hydroxy-Alkylphosphonates

Molecules, Год журнала: 2025, Номер 30(2), С. 428 - 428

Опубликована: Янв. 20, 2025

A series of α-hydroxy-alkylphosphonates and α-hydroxy-alkylphosphine oxides were synthesized by the Pudovik reaction acetaldehyde acetone with dialkyl phosphites or diarylphosphine oxides. The additions performed in three different ways: liquid phase using triethylamine as catalyst (1), on surface Al2O3/KF solid (2), a MW-assisted Na2CO3-catalyzed procedure (3). In most cases, our methods more efficient robust than those applied literature. Two subjected to single-crystal X-ray analysis, suggesting dimeric chain supramolecular buildup their respective crystals. Four one α-hydroxy-ethylphosphine oxide reacted acid chlorides afford ten α-acyloxyphosphonates. Diethyl α-hydroxy-ethylphosphonate was transformed methanesulfonyloxy derivative that useful Michaelis–Arbuzov triethyl phosphite ethyl diphenylphosphinite tetraethyl ethylidenebisphosphonate diethyl α-(diphenylphosphinoyl)-ethylphosphonate, respectively. α-hydroxyphosphonates α-hydroxyphosphine prepared bioactivity studies, compounds tested exhibited limited cytotoxic effects U266 cells modest reductions viability at concentration 100 μM.

Язык: Английский

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Ligand-enabled override of the memory effect in Rh-catalyzed asymmetric Suzuki reactions

Chem, Год журнала: 2025, Номер unknown, С. 102550 - 102550

Опубликована: Апрель 1, 2025

Язык: Английский

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Synthesis of vinyl-substituted alcohols using acetylene as a C2 building block

Chemical Science, Год журнала: 2022, Номер 14(7), С. 1912 - 1918

Опубликована: Дек. 23, 2022

Vinyl-substituted alcohols represent a highly useful class of molecular skeletons. The current method typically requires either stoichiometric metallic reagents or preformed precursors. Herein, we report nickel catalysis-enabled synthesis vinyl-substituted via 5-membered oxa-metallacycle. In this protocol, acetylene, the simplest alkyne and abundant feedstock, is employed as an ideal C2 synthon. reaction features mild conditions, good functional group tolerance broad substrate scope. Mechanistic exploration implies that oxa-metallacycle originated from cyclometallation aldehyde acetylene key intermediate for transformation, which then terminated by silane-mediated σ-bond metathesis subsequent reductive elimination.

Язык: Английский

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Tridentate Sulfoxide-N-olefin Hybrid Ligands in Rhodium-Catalyzed Asymmetric Allylic Substitution

Organic Letters, Год журнала: 2024, Номер 26(9), С. 1970 - 1974

Опубликована: Фев. 29, 2024

A well-defined tridentate chiral sulfoxide-N-olefin ligand has been designed and applied in rhodium-catalyzed asymmetric allylic substitutions of racemic carbonates, providing the branched products good yields with to high enantioselectivities excellent regioselectivities. This reaction mechanism, which involves possible hemilability olefin coordination on hybrid ligands rhodium, is elaborated as well.

Язык: Английский

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Rhodium-Catalyzed Asymmetric N²-C5 Allylation of Indazoles with Dienyl Allylic Alcohols

Organic Letters, Год журнала: 2024, Номер 26(27), С. 5646 - 5651

Опубликована: Июль 2, 2024

The development of site-selective and regio- enantioselective reactions substrates with multiple active sites is an important topic remains a substantial challenge in synthetic chemistry. Here, we describe rhodium-catalyzed asymmetric

Язык: Английский

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A General Enantioselective α-Alkyl Amino Acid Derivatives Synthesis Enabled by Cobalt-Catalyzed Reductive Addition

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 12, 2024

Enantioenriched unnatural amino acids represent a prevalent motif in organic chemistry, with profound applications biochemistry, medicinal and materials science. Herein, we report cobalt-catalyzed aza-Barbier reaction of dehydroglycines unactivated alkyl halides to afford α-amino esters high enantioselectivity. This catalytic reductive alkylative addition protocol circumvents the use moisture-, air-sensitive organometallic reagents, stoichiometric chiral auxiliaries, enabling conversion variety primary, secondary, even tertiary α-alkyl-amino under mild conditions, thus leading broad functional group tolerance. The expedient access biologically active motifs demonstrates practicality this by reducing number synthetic steps enhancing efficiency.

Язык: Английский

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Rhodium-Catalyzed Regio- and Enantioselective Allylic Sulfonylation from Sulfonyl Hydrazides

Organic Letters, Год журнала: 2023, Номер 25(20), С. 3693 - 3697

Опубликована: Май 15, 2023

A highly regio- and enantioselective allylic sulfonylation has been developed with rhodium bisoxazolinephosphine (NPN*) ligands from racemic branched carbonates readily available sulfonyl hydrazides under neutral conditions. Branch-selective sulfones a >20:1 branch:linear ratio >99% ee could be synthesized in ≤96% yield. Both Z E linear also converted into the same chiral high enantioselectivities.

Язык: Английский

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Secondary Phosphine Sulfide‐Enabled Iridium‐Catalyzed Asymmetric Allylic Substitution

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(52)

Опубликована: Окт. 28, 2022

An iridium-catalyzed asymmetric synthesis of branched allylic phosphine compounds under mild conditions is reported. Products bearing various functional groups can be synthesized with excellent stereoselectivity (up to 99.9 % ee) and regioselectivity. The employment sulfides relatively low deactivation capacity against metal catalysts crucial for the success this reaction.

Язык: Английский

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Asymmetric Formal Abnormal Claisen Rearrangement Enabled by Rh-Catalyzed Regio- and Enantioselective Allylic Alkylation

ACS Catalysis, Год журнала: 2023, Номер 13(8), С. 5482 - 5490

Опубликована: Апрель 7, 2023

Abnormal Claisen rearrangement of phenyl allyl ether with the γ-alkyl group is longstanding. However, asymmetric version this named reaction has never been reported. Herein, a highly regio- and enantioselective allylic alkylation 4-hydroxycoumarin stereospecific Conia-ene/ene sequence developed as formal abnormal rearrangement. Chiral 4-hydroxycoumarins 3-allyl groups could be synthesized in up to 95% yield 96% ee under catalysis Rh chiral bioxazolinephosphine ligand. Experimental density functional theory calculation investigations support that based on reversible formation kinetically favored cis-disubstituted spirocyclopropane intermediate.

Язык: Английский

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A computational study on cobalt-catalyzed allylic substitution of racemic allylic carbonates with amines: inner-sphere C–N reductive elimination and origins of regio- and enantioselectivities

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(12), С. 2976 - 2987

Опубликована: Янв. 1, 2023

DFT calculations reveal an inner-sphere C–N reductive elimination pathway for the cobalt/bisoxazolinephosphine-catalyzed allylic substitution of racemic carbonates with amines.

Язык: Английский

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