Bulky P-stereogenic ligands. A success story in asymmetric catalysis

Coordination Chemistry Reviews, Год журнала: 2023, Номер 489, С. 215192 - 215192

Опубликована: Май 9, 2023

Since the development of BisP* ligand by Imamoto, P-stereogenic phosphines bearing a bulky tert-butyl group and smaller alkyl have demonstrated extraordinary proficiency in wide range asymmetric processes. Over time, this class ligands has brought about introduction more rigid backbones, three-hindered quadrant concept, substitution adamantyl. The methyl fragment also been introduced phosphino-oxazoline-type ligands, chemists industrial sector contributed to evolution reporting first successful Buchwald-type monophosphines for coupling reactions. present review covers synthesis applications that developed since advent late 1990s, with special emphasis on successfully applied catalysis.

Язык: Английский

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Catalytic Asymmetric Hydrophosphinylation of 2‐Vinylazaarenes to Access P‐Chiral 2‐Azaaryl‐Ethylphosphine Oxides

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(16)

Опубликована: Фев. 22, 2023

A chiral Brønsted acid-catalysed asymmetric hydrophosphinylation of 2-vinylazaarenes by secondary phosphine oxides is described. variety P-chiral 2-azaaryl-ethylphosphine are synthesized with high yields and ees, which both the substituents phosphines azaarenes can be flexibly modulated, underscoring an exceptionally broad scope substrates. These adducts valuable to metal catalysis since resultant tertiary from reduction them verified as a kind effective C1 -symmetric 1,5-hybrid P,N-ligands. Importantly, this platform enables generic efficient kinetic resolution oxides. It thus provides expedient approach access enantiomers derived hydrophosphinylation, further improving utility method.

Язык: Английский

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Copper-Catalyzed Dynamic Kinetic Resolution of Secondary Phosphine Oxides

Organic Letters, Год журнала: 2023, Номер 25(13), С. 2178 - 2183

Опубликована: Фев. 10, 2023

Copper-catalyzed dynamic kinetic resolution of secondary phosphine oxides has been successfully developed, providing a general method for the gram-scale enantioselective synthesis P-stereogenic cyclic with high yields and enantioselectivities. The products could be easily reduced to corresponding useful P(III)-stereogenic phosphines. A mechanism involving unusual rapid racemization SPOs proposed.

Язык: Английский

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Ni^II-Catalyzed Enantioselective Anti-Markovnikov Hydrophosphination of Unactivated Alkynes

ACS Catalysis, Год журнала: 2023, Номер 13(10), С. 6994 - 7001

Опубликована: Май 9, 2023

A mechanism-inspired, reaction mode-controlled enantio- and regioselective anti-Markovnikov hydrophosphination of unactivated alkynes was accomplished by NiII catalysis. Alkenyl phosphine products could be obtained with high regio- enantioselectivity easily derivatized to structurally diverse chiral compounds. Mechanistic studies on both Ni0-catalyzed Markovnikov addition NiII-catalyzed have been carried out combining experimental computational methods. In the Ni0 system, an allyl nickel complex as catalyst resting state whose structure unambiguously determined single-crystal XRD analysis. sequential hydrometallation, ligand exchange, reductive elimination mechanism elucidated corroboratively DFT calculations. cationic secondary serves active catalyst. migratory insertion protonation sequence operative accomplish hydrophosphination.

Язык: Английский

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Copper‐Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июнь 19, 2023

We describe a copper catalyst that promotes the addition of phosphines to cyclopropenes at ambient temperature. A range cyclopropylphosphines bearing different steric and electronic properties can now be accessed in high yields enantioselectivities. Enrichment phosphorus stereocenters is also demonstrated via Dynamic Kinetic Asymmetric Transformation (DyKAT) process. combined experimental theoretical mechanistic study supports an elementary step featuring insertion Cu

Язык: Английский

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Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(18)

Опубликована: Фев. 21, 2024

A broadly improved second generation catalytic two-phase strategy for the enantioselective synthesis of stereogenic at phosphorus (V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows divergent access to wide range C-, N-, O- S- substituted containing from handful enantioenriched intermediates. new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be transformed into an even greater distinct classes by displacement remaining as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP-catalyzed desymmetrization, rationalize how superior catalyst/leaving leads generality in our second-generation system, shed light onto observed stereochemical retention inversion pathways when performing late-stage S

Язык: Английский

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Palladium-catalyzed regio- and stereo-selective phosphination of cyclic biarylsulfonium salts to access atropoisomeric phosphines

Chemical Science, Год журнала: 2024, Номер 15(18), С. 6943 - 6948

Опубликована: Янв. 1, 2024

A Pd-catalyzed atroposelective phosphination of cyclic biarylsulfonium salts with HPAr 3 Ar 4 for straightforward synthesis chiral phosphines bearing a stereogenic axis or both and P-stereogenic center is reported.

Язык: Английский

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Iridium-Catalyzed Enantioselective C–H Borylation of Diarylphosphinates

ACS Catalysis, Год журнала: 2021, Номер 11(21), С. 13445 - 13451

Опубликована: Окт. 21, 2021

P-stereogenic phosphorus compounds are a ubiquitous and critically important class of chiral ligands in asymmetric catalysis. Methods for catalytic synthesis via step- atom-economic way still very limited. We herein disclose protocol phosphinate-directed iridium-catalyzed enantioselective ortho-H borylation to construct compounds. A number functional groups could be well tolerated afford optically active diarylphosphinates with good excellent enantioselectivities (up 92% ee). also demonstrate the synthetic utilities obtained borylated products, including precursors phosphine ligands.

Язык: Английский

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Ni-Catalyzed Enantioselective Allylic Alkylation of H-Phosphinates

Organic Letters, Год журнала: 2021, Номер 23(22), С. 8683 - 8687

Опубликована: Ноя. 4, 2021

The asymmetric synthesis of P-stereogenic phosphinates through allylic alkylation H-phosphinates has been developed. With and acetates as the starting materials, a variety P-chiral were accessed in high enantioselectivities up to 92% ee generally yields. In addition, further study demonstrated applicability this protocol, including scale-up facile transformation chiral products from phosphine oxides with organolithium reagents under mild reaction conditions.

Язык: Английский

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Nickel/Brønsted acid dual-catalyzed regio- and enantioselective hydrophosphinylation of 1,3-dienes: access to chiral allylic phosphine oxides

Chemical Science, Год журнала: 2021, Номер 13(5), С. 1390 - 1397

Опубликована: Дек. 28, 2021

While chiral allylic organophosphorus compounds are widely utilized in asymmetric catalysis and for accessing bioactive molecules, their synthetic methods still very limited. We report the development of nickel/Brønsted acid dual-catalyzed hydrophosphinylation 1,3-dienes with phosphine oxides. This reaction is characterized by an inexpensive catalyst, broad substrate scope, high regio- enantioselectivity. study allows construction oxides a highly economic efficient manner. Preliminary mechanistic investigations suggest that 1,3-diene insertion into Ni-H species regioselective process formation C-P bond irreversible step.

Язык: Английский

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