Elsevier eBooks, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
Language: Английский
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 6422 - 6437
Published: March 1, 2024
The development of a new catalytic strategy plays vital role in modern organic chemistry since it permits bond formation an unprecedented and more efficient manner. Although the application preformed metal complexes as π-base-activated reagents have enabled diverse transformations elegantly, concept by directly utilizing transition metals π-Lewis base catalysts remain underdeveloped, especially field asymmetric catalysis. Here, we outline our perspective on discovery palladium(0) catalyst, which is capable increasing highest occupied molecular orbital (HOMO) energy both electron-neutral electron-deficient 1,3-dienes 1,3-enynes upon flexible η2-complexes formed situ resultant π-backdonation. Thus, fruitful carbon–carbon-forming reactions with electrophiles can be achieved enantioselectively vinylogous addition pattern, conceptually different from classical oxidative cyclization mechanism. Emphasis will given to mechanism elucidation, features, reaction design together further this emerging field.
Language: Английский
Citations
14
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 6936 - 6946
Published: Feb. 28, 2024
Here, we describe a cooperative Pd(0)/chiral phosphoric acid catalytic system that allows us to realize the first chemo-, regio-, and enantioselective sequential cross-[4 + 2]-cycloaddition/decarboxylation reaction between 2-pyrones unactivated acyclic 1,3-dienes. The key success of this transformation is utilization an achiral N-heterocyclic carbene (NHC) as ligand newly developed chiral cocatalyst. Experimental investigations computational studies support idea Pd(0)/NHC complex acts π-Lewis base increase nucleophilicity 1,3-dienes via η2 coordination, while simultaneously increases electrophilicity by hydrogen bonding. By synergistic catalysis, 2]-cycloaddition decarboxylation proceeds efficiently, enabling preparation wide range vinyl-substituted 1,3-cyclohexadienes in good yields enantioselectivities. synthetic utility demonstrated transformations product various valuable six-membered carbocycles.
Language: Английский
Citations
6
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(10), P. 5624 - 5630
Published: March 2, 2023
A cooperative catalyst system involving a Pd(0)/Senphos complex, tris(pentafluorophenyl)borane, copper bromide, and an amine base, is demonstrated to catalyze trans-hydroalkynylation of internal 1,3-enynes. For the first time, Lewis acid shown promote reaction emerging outer-sphere oxidative step. The resulting cross-conjugated dieneynes are versatile synthons for organic synthesis, their characterization reveals distinct photophysical properties depending on positioning donor/acceptor substituents along conjugation path.
Language: Английский
Citations
15
Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(4), P. 1915 - 1935
Published: Jan. 1, 2024
This review summarizes the recent advances in synthesis of transition metal borataalkene and boraalkene complexes, η 2 -B,C coordination mode homogeneous catalysis.
Language: Английский
Citations
2
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21638 - 21645
Published: Sept. 22, 2023
A method for the synthesis of allenes by addition ketones to 1,3-enynes cooperative Pd(0)Senphos/B(C6F5)3/NR3 catalysis is described. wide range aryl- and aliphatic undergo various in high yields at room temperature. Mechanistic investigations revealed a rate-determining outer-sphere proton transfer mechanism, which was corroborated DFT calculations.
Language: Английский
Citations
6
Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
A palladium-catalysed three-component reaction between 1,3-enynes, 2-formylphenylboronic acids and N -sulfonyl amines has been developed, furnishing a variety of multifunctional benzofulvenes in moderate to good yields E / Z -selectivity.
Language: Английский
Citations
1
Langmuir, Journal Year: 2024, Volume and Issue: 40(37), P. 19458 - 19466
Published: Sept. 3, 2024
Electrochemistry of outer-sphere redox molecules involves an essentially intact primary coordination sphere with minimal secondary adjustments, resulting in very fast electron transfer events even without a noble metal-based electrocatalyst. Departing from conventional electrocatalytic paradigms, we incorporate these reaction coordinate adjustments species to stimulate the electrocatalysis energetically challenging inner-sphere substrates. Through this approach, are able show intricate 8e
Language: Английский
Citations
1
Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(13), P. 3300 - 3306
Published: Jan. 1, 2023
Substrate-controlled divergent cascade reactions between ortho -vinyl-functionalised 1,3-enynes and imines have been realised via palladium catalysis, furnishing collections of skeletally distinct architectures in good yields stereoselectivity.
Language: Английский
Citations
3
Asian Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 12(6)
Published: May 18, 2023
Abstract Presented herein is a palladium catalyzed tandem reaction between 3‐aminoethyl group tethered 1,3‐enynes and imines, proceeding through cascade vinylogous addition/reductive elimination/protonation/allylic amination 1,3‐hydrogen transfer sequence. A collection of complex hexahydro‐1 H ‐pyrrolo[3,2‐ c ]pyridine architectures were straightforwardly constructed in moderate yields diastereoselectivity.
Language: Английский
Citations
2
Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(5), P. 1480 - 1480
Published: Jan. 1, 2024
Language: Английский
Citations
0