Direct synthesis of adipic acid esters via palladium-catalyzed carbonylation of 1,3-dienes

Science, Год журнала: 2019, Номер 366(6472), С. 1514 - 1517

Опубликована: Дек. 20, 2019

A carbonylation path to a nylon precursor Adipic acid and its esters are manufactured on massive scale, primarily produce nylon. However, the standard route requires large quantities of corrosive nitric acid. J. Yang et al. present an efficient alternative whereby palladium catalyst adds carbon monoxide each end butadiene (see Perspective by Schaub). Both reactants available at commodity reaction produces no by-products. An optimized bidentate phosphine ligand bearing pyridine substituent for proton shuttling proved key attaining necessary selectivity. Science , this issue p. 1514 ; see also 1447

Язык: Английский

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Cobalt‐Catalysed Asymmetric Addition and Alkylation of Secondary Phosphine Oxides for the Synthesis of P‐Stereogenic Compounds

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(52), С. 27241 - 27246

Опубликована: Ноя. 5, 2021

The catalytic asymmetric synthesis of P-chiral phosphorus compounds is an important way to construct ligands. Herein, we report a new strategy that adopts the pyridinyl moiety as coordinating group in cobalt-catalysed nucleophilic addition/alkylation secondary phosphine oxides. A series tertiary oxides were generated with up 99 % yield and 99.5 ee, broad functional-group tolerance. Mechanistic studies reveal (R)-secondary preferentially interact cobalt catalysts produce P-stereogenic compounds.

Язык: Английский

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State-of-the-art palladium-catalyzed alkoxycarbonylations

Organic Chemistry Frontiers, Год журнала: 2020, Номер 8(4), С. 799 - 811

Опубликована: Ноя. 19, 2020

State-of-the-art Pd-catalyzed alkoxycarbonylation: catalyst development and applications.

Язык: Английский

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Stereoselective synthesis of substituted 1,3-dienes from propargylic esters: electrophilic-metal or redox catalysis?

Science China Chemistry, Год журнала: 2024, Номер 67(5), С. 1384 - 1396

Опубликована: Март 22, 2024

Язык: Английский

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Kinetic Resolution of α,β-Unsaturated Tertiary Phosphine Oxides via Alkene E → Z Isomerization Catalyzed by a Photoexcited Chiral Copper Complex

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4541 - 4549

Опубликована: Март 3, 2025

Язык: Английский

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Asymmetric Hydroesterification of Diarylmethyl Carbinols

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(12), С. 6305 - 6309

Опубликована: Дек. 17, 2020

Abstract An efficient asymmetric hydroesterfication of diarylmethyl carbinols is developed for the first time with a Pd‐WingPhos catalyst, resulting in series chiral 4‐aryl‐3,4‐dihydrocoumarins excellent enantioselectivities and good yields. The method features mild reaction conditions, broad substrate scope, use easily accessible starting materials, low palladium loadings. A plausible stereochemical model also proposed catalyst. This has enabled 4‐step synthesis ( R )‐tolterodine from readily available materials.

Язык: Английский

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Tailored Palladium Catalysts for Selective Synthesis of Conjugated Enynes by Monocarbonylation of 1,3‐Diynes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(23), С. 9032 - 9040

Опубликована: Фев. 13, 2020

For the first time, monoalkoxycarbonylation of easily available 1,3-diynes to give synthetically useful conjugated enynes has been realized. Key success was design and utilization new ligand 2,2'-bis(tert-butyl(pyridin-2-yl)phosphanyl)-1,1'-binaphthalene (Neolephos), which permits palladium-catalyzed selective carbonylation under mild conditions, providing a general preparation functionalized 1,3-enynes in good-to-high yields with excellent chemoselectivities. Synthetic applications that showcase possibilities this novel methodology include an efficient one-pot synthesis 4-aryl-4H-pyrans as well rapid construction various heterocyclic, bicyclic, polycyclic compounds.

Язык: Английский

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Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(17), С. 9527 - 9533

Опубликована: Янв. 15, 2021

Abstract The dicarbonylation of 1,3‐butadiene to adipic acid derivatives offers the potential for a more cost‐efficient and environmentally benign industrial process. However, complex reaction network regioisomeric carbonylation isomerization pathways, make selective direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium‐catalysed process in presence 1,2‐bis‐di‐ tert ‐butylphosphin‐oxylene (d t bpx) ligands, which allow adipate diester formation from 1,3‐butadiene, carbon monoxide, methanol with 97 % selectivity 100 atom‐economy under scalable conditions. Under optimal conditions variety di‐ triesters 1,2‐ 1,3‐dienes can be obtained good excellent yields.

Язык: Английский

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Dimeric Manganese‐Catalyzed Hydroalkenylation of Alkynes with a Versatile Silicon‐Based Directing Group

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(31)

Опубликована: Июнь 7, 2023

Herein, we present a manganese-catalyzed, branched-selective hydroalkenylation of terminal alkynes, under mild conditions through facile installation versatile silanol as removable directing group. With an alkenyl boronic acid the coupling partner, this reaction produces stereodefined (E,E)-1,3-dienes with high regio-, chemo- and stereoselectivity. The protocol features such room temperature air atmosphere, while maintaining excellent functional group compatibility. resulting 1,3-dienesilanol products serve building blocks, removal allows for synthesis both branched 1,3-dienes downstream reactions, well stereoselective construction linear (E,E,E)- or (E,E,Z)-1,3,5-trienes. In addition, Diels-Alder cycloaddition can smoothly selectively deliver silicon-containing pentasubstituted cyclohexene derivatives. Mechanistic investigations, in conjunction DFT calculations, suggest bimetallic synergistic activation model to account observed enhanced catalytic efficiency good regioselectivity.

Язык: Английский

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Regiodivergent and Stereoselective Synthesis of Highly Substituted 1,3-Dienes via Arylative Acyloxy Migration of Propargyl Esters

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 18115 - 18125

Опубликована: Авг. 1, 2023

We report the first catalyst-controlled regiodivergent method that enables synthesis of structurally diverse 1,2,3,4-tetrasubstituted conjugated dienes with excellent regio- and stereochemical outcomes from same set readily available propargyl esters diaryliodonium salts. In this diene chemistry, in situ generated, highly electrophilic aryl-CuIII complex serves not only as a π-Lewis acid catalyst for alkyne activation/acyloxy migration but also an aryl electrophile equivalent. The competitive arylative 1,2- 1,3-acyloxy patterns are exquisitely dictated by Cu Au/Cu relay catalyses, respectively, providing modular attractive approach to traditionally inaccessible tetrasubstituted 1,3-dienes manner. Finally, synthetic utility is demonstrated further derivatization into array useful compounds.

Язык: Английский

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