Palladium/Xiao‐Phos‐Catalyzed Kinetic Resolution of sec‐Phosphine Oxides by P‐Benzylation

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(52), С. 27247 - 27252

Опубликована: Окт. 21, 2021

P-stereogenic tert- and sec-phosphines have wide applications in asymmetric catalysis, materials, pharmaceutical chemistry, however, their practical synthesis still constitutes a significant challenge. Herein, successful kinetic resolution of rac-secondary phosphine oxides via the enantioselective P-benzylation process catalyzed by palladium/Xiao-Phos was designed. Both sec-phosphine were delivered good yield excellent enantiopurity (selectivity factor up to 226.1). The appealing synthetic utilities are further demonstrated facile preparation several valuable P-chiral compounds, precursors bidentate ligands, as well transition metal complexes.

Язык: Английский

---

Novel Stereo‐Induction Pattern in Pudovik Addition/Phospha‐Brook Rearrangement Towards Chiral Trisubstituted Allenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(22)

Опубликована: Март 23, 2024

Abstract Despite the significance of chiral allene skeletons in catalysis, organic synthesis and medicinal chemistry et al., there is a scarcity reports on axially allenyl phosphorus compounds. Here, we disclosed an efficient straightforward cascade reaction between ethynyl ketones phosphine oxides, resulting broad array trisubstituted allenes incorporating moiety high yields with excellent stereoselectivities facilitated by peptide‐mimic phosphonium salt (PPS) Additionally, comprehensive series mechanistic experiments have been conducted to elucidate that this proceeds via asymmetric Pudovik addition followed subsequent phospha ‐Brook rearrangement occurs concomitantly kinetic resolution, representing stereospecific protonation process facilitating central‐to‐axial chirality transfer manner. We anticipate our research will pave way for promising exploration novel stereo‐induction pattern addition/ reaction.

Язык: Английский

---

Direct carbonyl reductive functionalizations by diphenylphosphine oxide

Science Advances, Год журнала: 2025, Номер 11(6)

Опубликована: Фев. 7, 2025

Reductive functionalization of aldehydes and ketones is one the most challenging but ultimately rewarding areas in synthetic chemistry related sciences. We report a simple extremely versatile carbonyl reductive strategy achieving direct, highly selective, efficient amination, etherification, esterification, phosphinylation reactions (hetero)aryl ketones, which are or unattainable to achieve by traditional strategies, using only diphenylphosphine oxide an inorganic base. It enables modular synthesis functionally structurally diverse tertiary amines, ethers, esters, phosphine oxides, etc., as well pesticides, drug intermediates, pharmaceuticals. Compared phosphorus-mediated name reactions, this firstly transformed C═O bonds into C-element single bonds. Mechanistically, phosphinates formed undergo unconventional nucleophilic substitution at C atom within their C─O─P unit. Thus, work provides important strides field aldehydes/ketones, transformation, various fundamental reactions.

Язык: Английский

---

Tf₂O/DMSO-Promoted P–O and P–S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates

Organic Letters, Год журнала: 2021, Номер 23(5), С. 1541 - 1547

Опубликована: Фев. 24, 2021

A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- strong-oxidant-free strategy provides facile approach to great variety organophosphinates thiophosphates. The simple reaction system, good functional-group tolerance, broad substrate scope enable application this method modification natural products direct synthesis bioactive molecules flame retardants.

Язык: Английский

---

Selective and Controllable Defluorophosphination and Defluorophosphorylation of Trifluoromethylated Enones: An Auxiliary Function of the Carbonyl Group

Organic Letters, Год журнала: 2023, Номер 25(20), С. 3745 - 3749

Опубликована: Май 11, 2023

The auxiliary function of a carbonyl group in the tunable defluorophosphination and defluorophosphorylation trifluoromethylated enones with P(O)-containing compounds was demonstrated. Controlled replacement one or two fluorine atoms while maintaining high chemo- stereoselectivity achieved under mild conditions, thus enabling diversity-oriented synthesis skeletally diverse organophosphorus libraries─(Z)-difluoro-1,3-dien-1-yl phosphinates, (1Z,3E)-4-phosphoryl-4-fluoro-buta-1,3-dien-1-yl (E)-4-phosphoryl-4-fluoro-1,3-but-3-en-1-ones─in good yields excellent functional tolerance.

Язык: Английский

---

Unified synthesis of multiply arylated alkanes by catalytic deoxygenative transformation of diarylketones

Chemical Science, Год журнала: 2022, Номер 13(36), С. 10743 - 10751

Опубликована: Янв. 1, 2022

We succeeded in synthesizing five different types of multiply arylated alkanes from diarylketones a single step. The key for this method is the generation diarylphosphinates via phospha-Brook rearrangement ketones with phosphine oxide.

Язык: Английский

---

Sequential In Situ-Formed Kukhtin–Ramirez Adduct and P(NMe₂)₃-Catalyzed O-Phosphination of α-Dicarbonyls with P(O)–H

Organic Letters, Год журнала: 2023, Номер 25(42), С. 7595 - 7600

Опубликована: Окт. 13, 2023

O-Phosphination of α-dicarbonyls via sequential in situ formation a Kukhtin-Ramirez adduct and P(NMe2)3-catalyzed process has been exploited for the synthesis α-phosphoryloxy carbonyls. A range P(O)-H derivatives, including diarylphosphine oxides, arylphosphinates, phosphinates, are competent candidates to be introduced into this transformation, various carbonyls obtained. This approach possesses advantages mild conditions, simple operations, atom economy, high efficiency, gram-scale synthesis, which make it promising toolbox.

Язык: Английский

---

Construction of Phosphonyl and Sulfonyl 3‐Methylene‐Oxindoles via Nucleophilic Vinylic Substitution

ChemistrySelect, Год журнала: 2025, Номер 10(11)

Опубликована: Март 1, 2025

Abstract 3‐Methylene‐substituted oxindoles play crucial roles as pharmaceutically important reagents well valuable synthons in medicinal and organic synthesis. In this study, a uniform nucleophilic vinylic substitution (S N V) reaction for the construction of phosphonyl sulfonyl substituted 3‐methylene‐oxindole was developed with application ( E )‐3‐(nitromethylene) oxindole powerful precursor. addition, preliminary study revealed that these have potential applications both constructing intriguing molecules serving antibacterial agents.

Язык: Английский

---

Reductive Deuteration of Aldehydes/Ketones for the Synthesis of Monodeuterated Phosphinates and Derivatives Using D₂O as the Nucleophilic Deuterium Source

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 14, 2025

The ideal deuteration, for organic synthetic chemists, might include the use of a cheap deuterium source, mild operating conditions, and diverse transformations. We developed an umpolung sequence reductive deuteration aldehydes/ketones, affording synthetically useful monodeuterated phosphinates. further one-pot transformation plausible mechanism this reaction were studied.

Язык: Английский

---

Primary Amination of Ar₂P(O)–H with (NH₄)₂CO₃ as an Ammonia Source under Simple and Mild Conditions and Its Extension to the Construction of Various P–N or P–O Bonds

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(5), С. 3254 - 3264

Опубликована: Янв. 24, 2022

A facile and efficient method for the synthesis of primary phosphinamides from Ar2P(O)-H reagents with stable readily available ammonium carbonate as an ammonia source is disclosed herein first time. This ethyl bromoacetate-mediated amination proceeds smoothly under mild simple conditions, without any metal catalyst or oxidant. Moreover, this also appropriate reaction a variety amines, alcohols, phenols to construct P-N P-O bonds, features handy operation, good functional group tolerance, broad substrate scope.

Язык: Английский

---