Catalytic Stereoselective Multicomponent Reactions for the Synthesis of Spiro Derivatives: Recent Progress

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(46)

Опубликована: Ноя. 16, 2022

Abstract Spiro derivatives are important scaffolding substances found in many natural products and pharmaceuticals. In the last decade, numerous new approaches based on multicomponent reactions have been explored for selective efficient development of spiro using various organocatalytic transition metal‐based catalytic systems. This Review discusses pioneering advances field stereoselective preparation derivatives. These include Michael cascade cyclization reactions, cycloadditions, diastereoselective miscellaneous synthesis spiro‐hetero/carbocycles. Advances decade made it possible to synthesize compounds with good excellent stereoselectivity under appropriate reaction conditions. However, achieving high regioselectivity several described remains a challenge. Organocatalysts transition‐metal‐based catalysts play crucial role this milestone. Proposed mechanisms supporting evidence highlighted Review. The progress is immense. expected that synthetic methods will soon be developed can widely used spiro‐heterocycles/carbocycles.

Язык: Английский

---

Divergent Synthesis of Enantioenriched Silicon‐Stereogenic Benzyl−, Vinyl− and Borylsilanes via Asymmetric Aryl to Alkyl 1,5‐Palladium Migration

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июль 30, 2024

Functionalization of Si-bound methyl group provides an efficient access to diverse organosilanes. However, the asymmetric construction silicon-stereogenic architectures by functionalization has not yet been described despite recent significant progress in producing chiral silicon. Herein, we disclosed enantioselective silylmethyl involving aryl alkyl 1,5-palladium migration naphthalenes possessing enantioenriched stereogenic silicon center, which are inaccessible before. It is worthy note that realization induction at step metal itself remains challenging. Our study constitutes first reaction. The key success discovery and fine-tuning different substituents α,α,α,α-tetraaryl-1,3-dioxolane-4,5-dimethanol (TADDOL)-based phosphoramidites, ensure enantioselectivity desired reactivity.

Язык: Английский

---

The Development and Application of SPSiBox Ligands: Cu-Catalyzed Enantioselective Carbene Insertion of Ge–H Bonds

Опубликована: Фев. 1, 2024

A class of C2-symmetrical bisoxazoline ligands with a flexible chiral pocket has been developed, which could be readily prepared in three steps from enantiopure SPSiOLs. This type presented high level enantioselectivity for the Cu-catalyzed asymmetric carbene insertion Ge–H bonds α-trifluoromethyl diazo compounds, thus providing an efficient method preparation enantioenriched ogranogermanes. reac-tion features broad substrates scope, mild reaction conditions, excellent enantioselectivity, and low catalyst loading. Preliminary mechanistic studies un-veiled that this might undergo concerted mechanism, computational unveiled origin induction SPSiBox ligand.

Язык: Английский

---

Design and Synthesis of Chiral Spiro Monophosphinites with a 3-Oxo-1,1′-spirobiindane Scaffold and Their Application in Rhodium-Catalyzed Asymmetric Hydrogenation of Dehydroamino Acid Esters

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 15, 2025

A new class of chiral spiro monophosphinites, based on a unique non-C2-symmetric 3-oxo-1,1'-spirobiindane scaffold featuring large dihedral angle, has been effectively designed and synthesized. From readily accessible resources, these monophosphinites were synthesized via eight steps in 16-32% yields. Their excellent performance the rhodium-catalyzed asymmetric hydrogenation β-dehydroamino acid esters underscores critical impact angle enhancing activity enantioselectivity.

Язык: Английский

---

Cobalt-Catalyzed Regioselective Intramolecular Hydrosilylation of Olefins to Access Sila-heterocycles

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

An efficient and straightforward cobalt-catalyzed regioselective intramolecular hydrosilylation of olefins has been developed. Regioselectivity is controlled by the choice ligands substrates, which operate through two distinct mechanisms. This method successfully applied to both terminal internal alkenes phenyl alkyl tethers between silane alkene, demonstrating its versatility across a broad range substrates.

Язык: Английский

---

Chiral spirosiladiphosphines: ligand development and applications in Rh-catalyzed asymmetric hydrosilylation/cyclization of 1,6-enynes with enhanced reactivity

Chemical Science, Год журнала: 2023, Номер 14(17), С. 4641 - 4646

Опубликована: Янв. 1, 2023

Spirodiphosphines have been successfully applied in various asymmetric catalytic transformations. However, controlling the coordinating conformations by direct displacement of spiro atom remains elusive. Herein, we report application Si-centered spirodiphosphine (Si-SDP) ligands enantioselective hydrosilylation/cyclization 1,6-enynes. The Si-SDPs showed superior reactivity to existing C2-symmetric diphosphines, allowing generation a range chiral pyrrolidines with high yields and enantioselectivity (up 96% yield 92% ee) at room temperature low catalyst loading. mechanistic observations were consistent modified Chalk-Harrod mechanism, was further leveraged for room-temperature Rh-catalyzed hydrosilylation alkynes.

Язык: Английский

---

Recent Progress in the Synthesis of Silaspiranes

Chemistry - A European Journal, Год журнала: 2023, Номер 29(70)

Опубликована: Сен. 23, 2023

Abstract Silaspiranes bearing a spiro‐silicon center are promising ring frameworks for the synthesis of novel spirocyclic molecules possessing unique properties. Development efficient methods towards these structures has therefore attracted considerable attentions synthetic chemists. This minireview highlights representative advances in field, and is categorized into four parts according to formation strategies: cyclization, annulation, expansion cycloaddition.

Язык: Английский

---

Carbon-silicon-switch effect in enantioselective construction of silicon-stereogenic center from silacyclohexadienones

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

Опубликована: Ноя. 15, 2024

Carbon-silicon-switch strategy, replacing one specific carbon atom in organic molecules with a silicon, has garnered significant interest for developing new functional molecules. However, the influence of reaction regarding its selectivity and reactivity by carbon-silicon-switch strategy far less been investigated. Here we discover an unusual effect enantioselective construction silicon-stereogenic center. It is found that there change desymmetrization silacyclohexadienones using asymmetric conjugate addition or oxidative Heck aryl/alkyl nucleophiles when compared their analogues cyclohexadienones. Specifically, leads to reversal enantioselectivity arylzinc as nucleophile same chiral catalyst, results totally different arylboronic acid nucleophile. Control experiments density theory (DFT) calculations have shown comes from unique stereoelectronic feature silicon. Silicon incorporated into place under principle that, given they belong periodic group, could be similar. Here, authors perform desymmetrizations on silacyclohexenone analogue, two substrates yielding opposite enantiomers, showing our understanding similarities atoms incomplete.

Язык: Английский

---

Silicon‐Stereogenic Monohydrosilane: Synthesis and Applications

Angewandte Chemie, Год журнала: 2022, Номер 134(36)

Опубликована: Май 20, 2022

Abstract Optically active organosilanes have been demonstrated to be versatile chiral reagents in synthetic chemistry since the early seminal contributions by Sommer and Corriu. Among these silicon‐containing architectures, monohydrosilanes, which bear a Si−H bond, hold unique position because of their facile transformations through stereospecific Si–carbon or Si–heteroatom bond‐formation reactions. In addition, those compounds also leveraged as for alcohol resolution, auxiliaries, mechanistic probes, well potential optoelectronic materials. This Minireview comprehensively summarizes synthesis applications silicon‐stereogenic particularly advances transition‐metal‐catalyzed asymmetric this class functional molecules.

Язык: Английский

---

Enantioselective Nickel‐Catalyzed Hydrosilylation of 1,1‐Disubstituted Allenes

Angewandte Chemie, Год журнала: 2023, Номер 135(11)

Опубликована: Янв. 18, 2023

Abstract Here, we report the first example of Ni‐catalyzed asymmetric hydrosilylation 1,1‐disubstituted allenes with high level regioselectivities and enantioselectivities. The key to achieve this stereoselective reaction was development SPSiOL‐derived bisphosphite ligands (SPSiPO). This protocol features broad substrate scope, excellent functional group, heterocycle tolerance, thus provides a versatile method for construction enantioenriched tertiary allylsilanes in straightforward atom‐economic manner. DFT calculations were performed reveal mechanism origins enantioselectivity.

Язык: Английский

---