Direct synthesis of functionalized 3-pyrrolidines and 4-piperidines using the borrowing hydrogen methodology DOI Creative Commons
Malvina Larduinat, Jordan François, Maïwenn Jacolot

et al.

Published: Jan. 30, 2023

The Ir(III)-catalyzed synthesis of 3-pyrrolidinols and 4-piperidinols combining 1,2,4-butanetriol or 1,3,5-pentanetriol with primary amines was carried out. This borrowing hydrogen methodology (BH) further extended to the sequential diamination triols leading aza-pyrrolidines aza-piperidines

Language: Английский

Transition-Metal-Catalyzed C–C Bond Formation from C–C Activation DOI
Feijie Song,

Bi‐Qin Wang,

Zhang‐Jie Shi

et al.

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(21), P. 2867 - 2886

Published: Oct. 26, 2023

ConspectusC-C single bonds are ubiquitous in organic compounds. The activation and subsequent functionalization of C-C provide a unique opportunity to synthesize conventionally inaccessible molecules through the rearrangement carbon skeletons, often with favorable atom step economy. However, thermodynamically kinetically inert. Consequently, is particularly attractive yet challenging field chemistry. In past decade, we sought develop efficient strategies carry out transition-metal-catalyzed diverse cleavage/C-C forming reactions obtain some insights into intrinsic reactivities different bonds. With our efforts, readily available alcohols, carboxylic acids, ketones served as suitable substrates for catalytic coupling reactions, which reviewed this Account. 2009, observed Ni-catalyzed cross aryl nitriles arylboronic esters C-CN cleavage. Encouraged by these results, interested bond activation. Due their broad availability, then turned attention cleavage acids. Rhodium-catalyzed decarbonylative acids (hetero)arenes was achieved oxidative addition situ formed, more reactive mixed anhydrides Rh(I) without need oxidants that commonly required decarboxylative Subsequently, decarbonylation unstrained realized under Rh catalysis assisted N-containing directing groups. Following work, group exchange 2-fold By employing chelation strategy, Rh-catalyzed secondary benzyl alcohols also accomplished β-carbon elimination rhodium alcoholate intermediates. competing oxidation via β-hydrogen same intermediates suppressed five-membered rhodacycles formed after elimination. Different types transformations including Heck-type reaction alkenes, arylsilanes, Grignard-type aldehydes or imines, have been achieved, showing great potential formation These bond-forming complementary traditional couplings halides organometallic reagents. produce small byproducts. To improve economy, investigated strained-ring cyclic intermolecular cyclization benzocyclobutenones alkynes recently uncommon C1-C8 removable blocking strategy. intramolecular annulation benzocyclobutenols achieved. summary, developments demonstrate new further expand synthetic utility activation, efforts substrate scope achieve earth-abundant metal-catalyzed transformations.

Language: Английский

Citations

36
Valorization of bio-renewable glycerol by catalytic amination reactions DOI Creative Commons
Sandeep Kumawat,

Sunidhi Singh,

Tarun Kumar Bhatt

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(6), P. 3021 - 3038

Published: Jan. 1, 2024

Production of value-added chemicals from renewable feedstocks is an attractive platform to alleviate the shortage petroleum resources and minimize CO 2 emissions.

Language: Английский

Citations

7
Access to Saturated Aza‐Heterocycles using the Borrowing Hydrogen Methodology DOI Creative Commons
Maïwenn Jacolot, Florence Popowycz

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(10)

Published: Feb. 9, 2024

Abstract Borrowing hydrogen (BH) has reached a wide attention from the chemistry community as new opportunity to construct efficiently C−N bond (as well C−C or C−S bond). This straightforward strategy is usually supported by relevant organometallic catalysts, involved in dehydrogenation‐reduction processes. concept highlights specifically application of borrowing preparation saturated aza‐heterocycles (piperidines, pyrrolidines and piperazines) extensively present high‐added value molecules pharmaceutical industry over last 40 years using homogenous catalysis particular. A focus will be given appropriate metals (Ru, Ir more recently earth‐abundant metals) used for this transformation. An extension chiral induction order prepare enantiopure N ‐heterocycles also reported.

Language: Английский

Citations

6
Borrowing Hydrogen Mechanism in Amine Alkylation by Single Atom Nickel Catalysts DOI Creative Commons

Aurore E. F. Denjean,

Ainara Nova, David Balcells

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11332 - 11342

Published: July 15, 2024

The alkylation of amines with alcohols by borrowing hydrogen (BH) is a versatile synthetic route to various relevant compounds, including drugs and agrochemicals. atom economy this reaction, water as the sole byproduct, entails complex mechanism in which alcohol activation can follow multiple competing pathways. interest single catalysts (SACs) combining advantages homogeneous heterogeneous systems motivated computational study on BH catalyzed nickel SACs. We found that oxidation, charge, spin states system, well geometry support, all have strong influence mechanism. pyrrolic support was most reactive dicationic state nearly degenerate singlet triplet configurations. free energy catalyst hydrogenation H2 strongly correlated its reactivity, thus being useful descriptor. Further, followed an unusual reaction pathway takes delivers H equivalents, metal playing spectator role. This provides insights for further development

Language: Английский

Citations

6
Selective amination of furfuryl alcohol to furfurylamine over nickel catalysts promoted by alumina encapsulation DOI
Yuqing Wei, Hao Wang,

Yingxue Qin

et al.

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 491, P. 151954 - 151954

Published: May 5, 2024

Language: Английский

Citations

4
Molybdenum‐Catalyzed Asymmetric Amination of α‐Hydroxy Esters: Synthesis of α‐Amino Acids DOI Creative Commons
Shahida Perveen, Talat S. Rahman, Tariq Ali

et al.

Advanced Science, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Abstract Unnatural α‐amino acids are found in a wide variety of bioactive compounds ranging from proteins to pharmaceutical agents materials science. As result, the investigation efficient and simple methods for their synthesis is major purpose reaction development. In this study, it that catalyst based on molybdenum, an earth‐abundant transition metal, can facilitate amination readily accessible α‐hydroxy esters afford N ‐protected unnatural acid high yield. This process also enables enantioselective amination, which proceeds through cooperative catalysis chiral molybdenum complex with phosphoric (CPA), complements earlier procedures catalytic important class compounds. The obtained protected ester products directly useful or further utilized commercially available drugs analogs.

Language: Английский

Citations

0
Catalytic C-N bond strategies for green amination of biomass-derived molecules DOI
Yan Zhong, Feng Liu, Jingsha Li

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(22), P. 11019 - 11060

Published: Jan. 1, 2024

Recent advances in the amination of biomass-derived molecules to generate valuable nitrogenous chemicals by employing thermocatalysis, electrocatalysis and photocatalysis strategies are reviewed.

Language: Английский

Citations

3
Chemodivergent Dehydrogenative Coupling of Alcohols by 3d Metal Catalysts DOI

Sadhna Bansal,

Benudhar Punji

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(12)

Published: Feb. 19, 2024

Abstract Chemodivergent synthesis by transition metal catalysts is a straightforward and sustainable approach to achieving valuable organic compounds. Especially, the chemodivergent dehydrogenative couplings of alcohols with motifs develop various saturated unsaturated compounds are highly environmentally benign due reduced waste generation. In this concept review, we presented 3d (Mn, Fe, Co, Ni)‐catalyzed imines amines, carbonyl/alcohol compounds, nitriles, N ‐heterocycles, N‐/C‐alkylated indoles. The discussed reaction commanded two or three different products high chemoselectivity changing specific parameters, but keeping catalyst unchanged. Generally, acceptorless coupling (ADC) provides moieties, whereas borrowing‐hydrogen (BH) process results in

Language: Английский

Citations

3
S-Alkylation of dithiocarbamates via a hydrogen borrowing reaction strategy using alcohols as alkylating agents DOI

P. Hima,

Spandan Hati, Raju Dey

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(31), P. 6360 - 6367

Published: Jan. 1, 2023

S -Alkylation of dithiocarbamates using alcohols as alkylating agents via a hydrogen borrowing strategy hydroxyapatite-supported copper nanoparticles heterogeneous catalyst.

Language: Английский

Citations

7
Manganese-catalyzed C–C and C–N bond formation with alcohols via borrowing hydrogen or hydrogen auto-transfer DOI Creative Commons

Mohd Farhan Ansari,

Atul Kumar Maurya, Abhishek Kumar

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 1111 - 1166

Published: May 21, 2024

Transition-metal-mediated "borrowing hydrogen" also known as hydrogen auto-transfer reactions allow the sustainable construction of C-C and C-N bonds using alcohols donors. In recent years, manganese complexes have been explored efficient catalysts in these reactions. This review highlights significant progress made manganese-catalyzed bond-formation via auto-transfer, emphasizing importance this methodology synthesis strategies.

Language: Английский

Citations

2