Hydrodeuteroalkylation of Unactivated Olefins Using Thianthrenium Salts

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 13, 2024

Isotopically labeled alkanes play a crucial role in organic and pharmaceutical chemistry. While some deuterated methylating agents are readily available, the limited accessibility of other deuteroalkyl reagents has hindered synthesis corresponding products. In this study, we introduce nickel-catalyzed system that facilitates various deuterium-labeled through hydrodeuteroalkylation d2-labeled alkyl TT salts with unactivated alkenes. Diverging from traditional reagents, thianthrenium (TT) can effectively selectively deuterium at α position chains using D

Language: Английский

---

N-heterocyclic carbenes as bridgehead donors in metal pincer complexes

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 514, P. 215757 - 215757

Published: May 9, 2024

Language: Английский

---

Stereoconvergent and Enantioselective Synthesis of Z-Homoallylic Alcohols via Nickel-Catalyzed Reductive Coupling of Z/E-1,3-Dienes with Aldehydes

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22157 - 22165

Published: Aug. 5, 2024

Stereoconvergent reactions enable the transformation of mixed stereoisomers into well-defined, chiral products─a crucial strategy for handling

Language: Английский

---

Nickel-catalyzed acylzincation of allenes with organozincs and CO

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 31, 2023

Transition metal-catalyzed carbonylative reaction with CO gas are among the central task in organic synthesis, enabling construction of highly valuable carbonyl compound. Here, we show an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence allene and alkylzinc reagent 1 atm under mild conditions. This protocol is featured by broad functional group tolerance high selectivity, providing a rapid convenient synthetic method for diverse fully substituted benzotropone derivatives. Mechanistic studies reveal that installation cyano tethered to moiety enables regio- stereoselectivity this acylzincation allene, allowing selective formation three consecutive C-C bonds efficient manner.

Language: Английский

---

Nickel‐Catalyzed Regio‐ and Enantioselective Migratory Hydrocyanation of Internal Alkenes: Expanding the Scope to α,ω‐Diaryl Internal Alkenes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 25, 2024

Abstract Metal‐hydride‐catalyzed migratory functionalization of alkenes witnessed extensive development in the past few years. However, asymmetric version this reaction has remained largely underdeveloped owing to difficulty simultaneous control both regio‐ and stereoselectivity. In addition, exploring wider alkene substrate scope enable more synthetically valuable applications represents another challenge field. context, a nickel‐catalyzed hydrocyanation internal involving chain‐walking process is demonstrated. The exhibits excellent enantioselectivity, proceeds under mild conditions, delivers benzylic nitriles high yields. Even α,ω‐diaryl alkenes, which are known be one most challenging substrates type, could successfully converted desired products with good stereoselectivity by modifying electronic steric effects. Theoretical calculations suggest that η 3 ‐benzyl coordination mode aryl substituent (3,5‐(OMe) 2 C 6 H ) on diphosphite ligand key factors regulating enantioselectivity.

Language: Английский

---

Highly Stereoselective Synthesis of 1,3‐Enynes via Aryl to Vinyl 1,4‐Palladium Migration/Sonogashira Coupling Sequence

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(16)

Published: April 12, 2024

Abstract Alkynylation of alkenyl bromoarenes via aryl to vinyl 1,4‐palladium migration/copper‐free Sonogashira coupling sequence has been developed. This approach provides a facile methodology for the highly stereoselective synthesis multi‐substituted 1,3‐enynes in good excellent yields and regioselectivities.

Language: Английский

---

Regiodivergent Radical-Relay Alkene Dicarbofunctionalization

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 28624 - 28629

Published: Oct. 10, 2024

Herein, we report a regiodivergent 1,n-dicarbofunctionalization of unactivated olefins enabled by Ni-catalyzed radical relay that forges both C(

Language: Английский

---

NHC-catalyzed enantioselective radical reactions of enal and pyridinium salt: mechanism and origin of regio- and stereoselectivities

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(18), P. 5259 - 5266

Published: Jan. 1, 2023

The origin of regio- and stereoselectivities NHC-catalyzed enantioselective radical reactions an enal a pyridinium salt has been explored via theory for the first time.

Language: Английский

---

C–H Functionalization of Arenes via NHC-Supported Ni/Al Bimetallic Catalysis

Synthesis, Journal Year: 2023, Volume and Issue: 55(24), P. 4049 - 4061

Published: June 21, 2023

Abstract Despite the C–H functionalization of arenes offering an efficient synthetic route towards functionalized aromatic compounds with high atom- and step-economy, low reactivity bond makes this transformation rather challenging. Compared mono-metal catalysis, introduction bimetallic catalysis would greatly enhance selectivity transformation. In review, we highlight recent progress in via NHC-Ni/Al catalysis. The added aluminum as a co-catalyst activate arene through Lewis acid-base interaction, regioselectivity could be controlled synergism NHC-Ni Al. This strategy also applied enantioselective alkylation well-designed chiral NHC ligands. 1 Introduction 2 Addition to Alkynes Activation 3 Alkylation Ni/Al Bimetallic Catalysis 3.1 Racemic Hydroarylation Alkenes 3.2 Asymmetric 4 Conclusion Outlook

Language: Английский

---

Copper-Catalyzed Enantioselective Three-Component Fluoroalkylalkynylation of Unactivated Alkenes

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 1693 - 1703

Published: Jan. 16, 2025

The enantioselective three-component dicarbonfunctionalization of electronically unactivated alkenes continues to pose a significant challenge. In this work, copper-catalyzed highly regio- and fluoroalkylalkynylation with diverse terminal alkynes fluoroalkyl halides under mild conditions is developed. addition halides, Togni's reagent can also participate in the reaction, delivering chiral β-trifluoromethyl high enantioselectivities. This method exhibits good functional group tolerance, facilitating late-stage derivatization variety biologically active molecules. success chemistry was achieved by using bulky indene-substituted BOPA ligand. DFT calculations indicate that radical through fluorine-directed outer-sphere pathway. Mechanistic studies reveal amide crucial for achieving stereoselectivities because exclusive F···H hydrogen bonding between Mes on be formed stabilize Si-radical coupling transition state.

Language: Английский

---