Regio- and Diastereoselective Hydrophosphination and Hydroamidation of gem-Difluorocyclopropenes

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(8), P. 5442 - 5457

Published: April 3, 2024

In this study, concise, efficient, and modular hydrophosphinylation hydroamidation of gem-difluorocyclopropenes were disclosed in a mild transition-metal-free pattern. Through approach, phosphorus, nitrogen-containing gem-difluorocyclopropanes produced moderate to good yields with excellent regio- diastereoselectivity. Readily available nucleophilic reagents, along inexpensive inorganic bases, employed. Multiple synthetic applications, including gram-scale derivatization reactions modification bioactive molecules, subsequently elaborated.

Language: Английский

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Rh(iii)-catalyzed redox-neutral C–H [4 + 1] annulation of sulfoximines with α,α-difluoromethylene alkynes: diastereoselective synthesis of E-monofluoroalkenyl benzoisothiazole 1-oxides

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(23), P. 5916 - 5922

Published: Jan. 1, 2023

Rh( iii )-catalyzed redox-neutral C–H [4 + 1] annulation of sulfoximines with α,α-difluoromethylene alkynes has been realized to diastereoselectively build E -monofluoroalkenyl benzoisothiazole 1-oxides.

Language: Английский

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Cp*Ir(iii) and Cp*Rh(iii)-catalyzed annulation of salicylaldehydes with fluorinated vinyl tosylates

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(64), P. 8966 - 8969

Published: Jan. 1, 2022

A mild, selective and redox-neutral Cp*Ir(III)- Cp*Rh(III)-catalyzed C-H activation/annulation of salicylaldehydes with fluorovinyl tosylates is reported. The use monofluorovinyl tosylate favors the synthesis C2- C3-substitution-free chromones via activation/β-F elimination/annulation, whereas difluorovinyl leads to construction C2-fluoroalkoxy chromones. Mild reaction conditions good functional-group tolerance were observed. Further functionalization resulting halogenation, alkynylation, alkylation hydrocyanation was successfully realized.

Language: Английский

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General Access to Clavine Alkaloids via a Rhodium(I)‐Catalyzed Diastereoselective Hayashi‐Miyaura Reaction

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(6), P. 1397 - 1404

Published: Jan. 27, 2024

Abstract We report the development of diastereoselective rhodium(I)‐catalyzed intramolecular conjugate addition (Hayashi‐Miyaura reaction) robust and easily handled 4‐pinacolboronic ester D‐tryptophan derivatives tethering an activated alkene as acceptor. This methodology provides, access to functionalized chiral tricyclic core ergoline skeleton diastereoselectivity allows further modification for cyclization fused fourth ring present in several clavine alkaloids.

Language: Английский

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Practical conversion of gem-difluorocyclopropenes for the chemodivergent assembly of fluorinated heterocyclic frameworks

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(24), P. 10630 - 10637

Published: Jan. 1, 2023

A green method has been established by employing gem -difluorocyclopropylenes as versatile building blocks, leading to the chemodivergent formation of several fluorinated structural motifs including cyclopropapyrazolopyridines, indolizines etc .

Language: Английский

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Recent Advances in the Transformation of Difluorocyclopropenes^★

Acta Chimica Sinica, Journal Year: 2023, Volume and Issue: 81(5), P. 520 - 520

Published: Jan. 1, 2023

In recent years, organic reactions involving difluorocyclopropenes have attracted the attention of chemists and made great progress.The mainly include: (1) cyclization: a) transition-metal catalyzed C-H bond activation cyclization with directing groups; b) non-directing (2) hydrogenation reduction; (3) fluorination as "F" source reagents.In this paper, synthesis methods applications in past 10 years are summarized.The conversion emphasized.Additionally, aroused considerable interests both from a structural standpoint their participation various ring-opening reactions.Given increasing application cyclopropyl skeleton development drugs unarguable importance fluorinated compounds medicinal chemistry agrochemistry, it is no doubt that encountered into bioactive molecular at present lie among "emerging motifs".Although structurally diverse been witnessed decade, most widely used for preparation these include difluoromethylenation alkynes difluoromethylation heteroatom nucleophiles (such NaF, NaI, n BuN4X, etc.) difluorocarbene reagent, which can be generated precursors TMSCF3, TMSCF2X, Ph3P ＋ CF2CO2 -, TFDA, etc.).For transition metal-catalyzed difluorocyclopropenes, some common metal salts rhodium, ruthenium, copper, palladium, silver) catalysts.Moreover, metallic hydrogen (M-H) reduction strategy simple efficient method leading to difluorocyclopropanes, asymmetric achieved presence chiral ligands.In reactions, advantages cannot by traditional reagents direct functionalization hydroxyl groups polyhydroxyl alcohols).Of course, biggest disadvantage difluorocyclopropene fluorine lies its poor atomic economy, has criticized.Despite remarkable achievements there still many issues need addressed.For instance, rarely applied radical photocatalysis, electrocatalysis flow chemistry.Hopefully, gradually appear photo-and electro-catalyzed chemistry, related will also get more near future.

Language: Английский

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Simple nucleophile/H2O promoted defluorinative ring-opening of gem-difluorocyclopropenes

Green Synthesis and Catalysis, Journal Year: 2023, Volume and Issue: 5(1), P. 14 - 19

Published: Jan. 13, 2023

A novel defluorinative ring-opening of gem-difluorocyclopropenes is presented, providing a concise and efficient method for accessing 2-fluoropropenals 2-fluorobuta-1,3-dienes in moderate to good yields with excellent regio- stereoselectivities. The reaction performed under mild conditions no need using an excess amount nucleophilic reagents. Water plays crucial role this transformation.

Language: Английский

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Ring Transformation of Cyclopropenes to Benzo‐Fused Five‐Membered Oxa‐ and Aza‐Heterocycles via a Formal [4+1] Cyclization

Advanced Science, Journal Year: 2024, Volume and Issue: 11(40)

Published: Aug. 29, 2024

Abstract In the context of growing importance heterocyclic compounds across various disciplines, numerous strategies for their construction have emerged. Exploiting distinctive properties cyclopropenes, this study introduces an innovative approach synthesis benzo‐fused five‐membered oxa‐ and aza‐heterocycles through a formal [4+1] cyclization subsequent acid‐catalyzed intramolecular O ‐ to N rearrangement. These transformations exhibit mild reaction conditions wide substrate scope. The applications in late‐stage modification complex molecules potential PD‐L1 gene down‐regulator, make method highly appealing related fields. Combined experimental mechanistic studies DFT calculations demonstrate Rh(III)‐mediated sequential C─H coupling/π‐allylation/dynamically favorable ‐attack route.

Language: Английский

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Regiocontrolled Rh(III)-catalyzed C C coupling/C N cyclization mediated by distinctive 1,2-migratory insertion of gem‑difluoromethylene allenes: Reaction development and mechanistic insight

Chinese Chemical Letters, Journal Year: 2022, Volume and Issue: 34(5), P. 107849 - 107849

Published: Sept. 25, 2022

Language: Английский

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Palladium-Catalyzed Diversified Synthesis of Monofluorinated Alkenes from Allylic gem-Difluorides through Pd–OH Intermediate

Organic Letters, Journal Year: 2023, Volume and Issue: 25(50), P. 9064 - 9069

Published: Dec. 13, 2023

Significant advancements in synthesis of monofluoroalkenes via palladium-catalyzed reactions involving allylic gem-difluorides and diverse nucleophiles have been achieved. This method allows regioselective arylation, alkylation, allylation, alkenylation, hydrogenation gem-difluorides, yielding high Z-selectivity favorable product yields under mild conditions. Tolerating various functional groups, these transformations utilize a common Pd-OH intermediate. Additionally, employing triple Pd-catalyzed cross-coupling trisubstituted alkenes efficiently.

Language: Английский

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