Z-Selective Synthesis of Trisubstituted Alkenes by the HWE Reaction Using Modified Still–Gennari Type Reagents

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

Опубликована: Апрель 16, 2025

Application of new reagents in the Z-selective synthesis trisubstituted alkenes via modified Horner-Wadsworth-Emmons carbonyl olefination is presented. The tested are ethyl bis(1,1,1,3,3,3-hexafluoroisopropyl)phosphonoalkanoates, structurally similar to Still-Gennari type reagents. A set various Z-alkenes was obtained very high or quantitative yields with excellent Z-selectivity. Remarkably, procedure successful for Z-2-aryl-substituted cinnamic acid esters, maintaining exclusive Z-selectivity even at an increased temperature.

Язык: Английский

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Cu-Catalyzed Enantioselective Carbene Insertion into Ge–H and Si–H Bonds Enabled by SPSiBox with a Tunable Chiral Pocket

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 28, 2025

Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge-H and Si-H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed C2-symmetrical bisoxazoline ligands. This protocol provides an efficient method for preparation enantioenriched ogranogermanes organosilanes, featuring broad substrate scope, mild reaction conditions, excellent enantioselectivity, low catalyst loading. The key to tolerance is use SPSiBox ligands bearing flexible tunable chiral pocket. Preliminary mechanistic studies computational unveiled origin induction ligands, mechanism insertion. not only new construction trifluoromethyl-containing molecules but also opens avenue Si- Ge-containing functional molecules.

Язык: Английский

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Visible Light Induced B–H Bond Insertion Reaction with Diazo Compounds

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 12583 - 12590

Опубликована: Авг. 19, 2024

A protocol induced by visible light for the direct insertion of α-carbonyl carbenes into B–H bond amine-borane adducts has been developed under conditions that are free metal and photocatalyst. This approach provides a straightforward route to various organoboron compounds from diazo with moderate good yields. Mechanistic investigations reveal this photoinduced reaction proceeds through concerted carbene bond, generation α-diazo esters may be rate-determining step.

Язык: Английский

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Fe-catalyzed B–H and Si–H insertion reactions of gem-dihaloalkanes

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(8), С. 2241 - 2248

Опубликована: Янв. 1, 2024

We present an approach involving Fe-catalyzed B–H and Si–H insertion of gem -dichloroalkanes. In contrast to previous strategies, our method uses -dihaloalkanes as non-stabilized carbene precursors operates through a radical reaction pathway.

Язык: Английский

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Highly Selective Boron‐Wittig Reaction: a Practical Method to Synthesize Trans‐Aryl Alkenes

Chemistry - A European Journal, Год журнала: 2024, Номер unknown

Опубликована: Июль 27, 2024

Olefins play an essential role in synthetic chemistry, serving not only as important synthons but also key functional groups numerous bio-active molecules. Consequently, there has been considerable interest the development of more powerful methods for olefins. While Wittig reaction stands a prominent choice olefin synthesis due to its simplicity and ready availability raw materials, limitation lies challenge controlling cis-trans selectivity, hampering broader application. In this study, novel Boron-Wittig developed utilizing gem-bis(boryl)alkanes aldehydes starting materials. This method enables creating favourable intermediates, which possess less steric hindrance, leading trans-olefins via intramolecular O-B bonds elimination. Notably, studies have validated good efficacy modifying bioactive molecules synthesizing drug with great trans-selectivity. Furthermore, mechanism was elucidated based on intermediate trapping experiments, isotope labelling studies, kinetic analyses.

Язык: Английский

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Direct synthesis of α-functionalized amides via heteroatom–hydrogen insertion reactions using amide-sulfoxonium ylides

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 25, 2024

α-Functionalized Si-, Ge-, B-, Se-, and S-amide moieties are present in many medicinally active molecules, but their synthesis remains challenging. Here, we demonstrate a high-throughput using amide-sulfoxonium ylides as carbene precursors Si-H, Ge-H, B-H, Se-H, S-H insertion reactions to target wide range of α-silyl, α-geryl, α-boryl, α-selenyl, α-sulfur (hetero)amides. The process is featured simple operation, mild conditions, broad substrate scope, high functional group compatibility, excellent chemoselectivity. Both experimental computational studies conducted explore the mechanisms underlying formation C-Si/Ge/B/Se/S bond. This research highlights use highly selective X-H with ylide-derived carbenes, paving way for preparation diverse organosilane, organogermane, organoboron, organoselenium, organosulfur compounds from accessible bench-stable precursors.

Язык: Английский

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Rhodium-Catalyzed Synthesis of Trifluoromethyl-Containing Allylic Alcohols Via Z-Alkenyl Transfer with High Stereochemistry Retention

Organic Letters, Год журнала: 2024, Номер unknown

Опубликована: Дек. 9, 2024

Herein, we report the rhodium-catalyzed

Язык: Английский

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Enantioselective α-Boryl Carbene Transformations

Synlett, Год журнала: 2024, Номер unknown

Опубликована: Июнь 4, 2024

Abstract α-Boryl carbenes, which are hybrid structures combining elements of carbenes and boryl groups, represent promising intermediates for constructing organoboron compounds. However, these challenging to synthesize exhibit limited structural diversity. Moreover, their applications in asymmetric transformations remain largely unexplored. In this study, we utilized cyclopropenes as precursors rapidly α-Bpin metal a novel category critical the synthesis chiral molecules. Facilitated by copper complex modified bisoxazoline ligand, α-boryl participate range highly enantioselective transfer reactions, including B–H Si–H insertions, well cyclopropanation cyclopropanation/Cope rearrangement processes. This methodology provides access previously inaccessible, yet useful, organoborons, thereby significantly advancing both carbene chemistry. 1 Introduction 2 Previous Discovery Our Design 3 Copper Catalyzed Enantioselective Carbene Transfer Reactions 4 Mechanistic Studies 5 Conclusions

Язык: Английский

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Kinetically controlled Z-alkene synthesis using iron-catalysed allene dialkylation

Nature Synthesis, Год журнала: 2024, Номер unknown

Опубликована: Сен. 26, 2024

Язык: Английский

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