Visible Light-Induced Transition Metal Catalysis

Chemical Reviews, Год журнала: 2021, Номер 122(2), С. 1543 - 1625

Опубликована: Окт. 8, 2021

In recent years, visible light-induced transition metal catalysis has emerged as a new paradigm in organic photocatalysis, which led to the discovery of unprecedented transformations well improvement known reactions. this subfield complex serves double duty by harvesting photon energy and then enabling bond forming/breaking events mostly via single catalytic cycle, thus contrasting established dual photocatalysis an exogenous photosensitizer is employed. addition, approach often synergistically combines catalyst–substrate interaction with photoinduced process, feature that uncommon conventional photoredox chemistry. This Review describes early development advances emerging field.

Язык: Английский

---

Visible light photocatalysis in the late-stage functionalization of pharmaceutically relevant compounds

Chemical Society Reviews, Год журнала: 2020, Номер 50(2), С. 766 - 897

Опубликована: Дек. 22, 2020

Recent developments and future prospects of visible-light photocatalysis in the late-stage functionalization pharmaceuticals natural bioactive compounds.

Язык: Английский

---

Recent advances in multi-component reactions and their mechanistic insights: a triennium review

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(15), С. 4237 - 4287

Опубликована: Янв. 1, 2021

This review summarizes the recent developments in MCRs, incorporating different strategies along with their mechanistic aspects.

Язык: Английский

---

Transition Metal (Ni, Cu, Pd)-Catalyzed Alkene Dicarbofunctionalization Reactions

Accounts of Chemical Research, Год журнала: 2021, Номер 54(17), С. 3415 - 3437

Опубликована: Авг. 12, 2021

ConspectusRecently, alkene dicarbofunctionalization, i.e., the powerful organic synthesis method of difunctionalization with two carbon sources, emerged as a formidable reaction immense promise to synthesize complex molecules expeditiously from simple chemicals. This is generally achieved transition metals (TMs) through interception by sources an alkylmetal [β-H–C(sp3)–[M]] species, key intermediate prone undergo rapid β-H elimination. Related prior reports, since Paolo Chiusoli and Catellani's work in 1982 [ Tetrahedron Lett. 1982, 23, 4517], have used bicyclic disubstituted terminal alkenes, wherein elimination avoided geometric restriction or complete lack β-H's. With reasoning that β-H–C(sp3)–[M] intermediates could be rendered amenable use first row late TMs formation coordination-assisted transient metallacycles, these strategies were implemented address problem dicarbofunctionalization reactions.Because catalyze C(sp3)–C(sp3) coupling, Cu Ni anticipated impart sufficient stability intermediates, generated catalytically upon carbometalation, for their subsequent electrophiles/nucleophiles three-component reactions. Additionally, such innate property enable coupling partners entropically driven cyclization/coupling The cyclometalation concept stabilize intractable was hypothesized when reactions performed. idea curtail founded Whitesides's J. Am. Chem. Soc. 1976, 98, 6521] observation metallacycles much slower than acyclic alkylmetals.In this Account, examples demonstrate catalysts alkenylzinc reagents, alkyl halides, aryl halides afford carbo- heterocycles. In addition, forming nickellacycles enabled regioselective performance various alkenyl compounds. situ [M]-H alkenes after induced unprecedented metallacycle contraction process, which six-membered metal-containing rings shrank five-membered cycles, allowing creation new carbon–carbon bonds at allylic (1,3) positions. Applications are discussed.

Язык: Английский

---

Transition metal-catalysed allylic functionalization reactions involving radicals

Chemical Society Reviews, Год журнала: 2020, Номер 49(17), С. 6186 - 6197

Опубликована: Янв. 1, 2020

In this tutorial review, different types of transition metal-catalysed allylic functionalization reactions involving radicals are highlighted.

Язык: Английский

---

Bifunctional reagents in organic synthesis

Nature Reviews Chemistry, Год журнала: 2021, Номер 5(5), С. 301 - 321

Опубликована: Апрель 12, 2021

Язык: Английский

---

Photoinduced Copper-Catalyzed Asymmetric C–O Cross-Coupling

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(33), С. 13382 - 13392

Опубликована: Авг. 10, 2021

The construction of carbon–heteroatom bonds is one the most active areas research in organic chemistry because function molecules often derived from presence heteroatoms. Although considerable advances have recently been achieved radical-involved catalytic asymmetric C–N bond formation, there has little progress corresponding C–O bond-forming processes. Here, we describe a photoinduced copper-catalyzed cross-coupling readily available oxime esters and 1,3-dienes to generate diversely substituted allylic with high regio- enantioselectivity (>75 examples; up 95% ee). reaction proceeds at room temperature under excitation by purple light-emitting diodes (LEDs) features use single, earth-abundant copper-based chiral catalyst as both photoredox for radical generation source induction coupling. Combined experimental density functional theory (DFT) computational studies suggest formation π-allylcopper complexes redox-active bifunctional reagents through radical–polar crossover process.

Язык: Английский

---

Enantioselective Radical Carbocyanation of 1,3-Dienes via Photocatalytic Generation of Allylcopper Complexes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(11), С. 4168 - 4173

Опубликована: Март 11, 2021

1,3-Dienes are readily available feedstocks that widely used in the laboratory and industry. However, potential of converting 1,3-dienes into value-added products, especially chiral has not yet been fully exploited. By synergetic photoredox/copper catalysis, we achieve first visible-light-induced, enantioselective carbocyanation by using carboxylic acid derivatives trimethylsilyl cyanide. Under mild neutral conditions, a diverse range allyl cyanides produced generally good efficiency with high enantioselectivity from bench-stable user-safe chemicals. Moreover, preliminary results also confirm this success can be expanded to 1,3-enynes four-component carbonylative 1,3-enynes.

Язык: Английский

---

Photoinduced Copper‐Catalyzed Asymmetric Three‐Component Coupling of 1,3‐Dienes: An Alternative to Kharasch–Sosnovsky Reaction

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(42), С. 22956 - 22962

Опубликована: Авг. 18, 2021

Abstract Kharasch–Sosnovsky reaction is one of the most powerful methods for allylic oxidation alkenes. However, inherent radical mechanism and use peroxides as both oxidants oxygen nucleophiles render dearth universal catalytic systems highly enantioselective variants limited scope. Herein, an alternative to asymmetric that utilized a chiral copper catalyst purple‐LED irradiation enable three‐component coupling 1,3‐dienes, oxime esters, carboxylic acids reported. This protocol features mild conditions, remarkable scope functional group tolerance evidenced by >80 examples utility in late‐stage modification pharmaceuticals natural products. Detailed mechanistic studies provide evidences radical‐based pathway.

Язык: Английский

---

Asymmetric intermolecular allylic C–H amination of alkenes with aliphatic amines

Science, Год журнала: 2022, Номер 378(6625), С. 1207 - 1213

Опубликована: Дек. 15, 2022

Aliphatic allylic amines are found in a great variety of complex and biorelevant molecules. The direct C-H amination alkenes serves as the most straightforward method toward these motifs. However, use widely available internal with aliphatic this transformation remains synthetic challenge. In particular, palladium catalysis faces twin challenges inefficient coordination Pd(II) to but excessively tight therefore inhibitory by basic amines. We report general solution problems. developed protocol, contrast classical Pd(II/0) scenario, operates through blue light-induced Pd(0/I/II) manifold mild aryl bromide oxidant. This open-shell approach also enables enantio- diastereoselective amination.

Язык: Английский

---