Palladium Catalyzed Alternating Cooligomerization of Ethylene and Carbon Monoxide to Unsaturated Ketones

Cationic palladium catalysts have been used to cooligomerize ethylene and carbon monoxide. At high ethylene/CO ratios (m /m = 10:1) in methylene chloride as a solvent, unsaturated alternating cooligomers of the general structure R[C(O)CH2CH2]mH ( m ≥ 1 ; R ≡CH2=CH-, CH2=CHCH2CH2- and CH3CH = CHCH2-) were obtained for the first time. Single component catalyst precursors [(allyl)Pd(P^X )]+Y- (P^X = Ph2P(CH2)nC(= O )OR, Ph2P(CH2)2P(=O)Ph2, Ph2P(CH2)nPh2P(CH2)2S (=O )Ph, n = 1 - 3 , R = Me, Et; Y- = BF4-, SbF6- ) with bidentate P,O- and P,S-ligands as well as in situ catalysts with unfunctionalized phosphine ligands were used. With P"Bu3 as a ligand, selectivities for ethylvinylketone of 40% based on the CO converted were obtained. The hemilabile phosphino-ester and phosphinothiophene ligands behave like monodentate phosphines under catalytic conditions.

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Palladium-Catalyzed Three-Component Coupling Reaction of Benzyl Chlorides, Allyltributylstannane, and Carbon Monoxide: Efficient Synthesis of α,β-Unsaturated Ketones

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION) ◽

10.3724/sp.j.1088.2012.10930 ◽

2013 ◽

Vol 33 (3) ◽

pp. 523-529

Author(s):

Xin ZHANG ◽

Xiujuan FENG ◽

Hesong LIU ◽

Yuhu QIN ◽

Yao DAI

Keyword(s):

Carbon Monoxide ◽

Coupling Reaction ◽

Efficient Synthesis ◽

Unsaturated Ketones ◽

Benzyl Chlorides ◽

Palladium Catalyzed ◽

Three Component Coupling

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Palladium‐Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide

Angewandte Chemie International Edition ◽

10.1002/anie.202005891 ◽

2020 ◽

Vol 59 (41) ◽

pp. 17887-17896 ◽

Cited By ~ 2

Author(s):

Philip Boehm ◽

Sven Roediger ◽

Alessandro Bismuto ◽

Bill Morandi

Keyword(s):

Carbon Monoxide ◽

Palladium Catalyzed ◽

In Situ Generation ◽

Pseudo Halides

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Palladium-Catalyzed Hydroxycarbonylation of Aryl and Vinyl Triflates by in situ Generated Carbon Monoxide under Microwave Irradiation

Synthesis ◽

10.1055/s-2006-926288 ◽

2006 ◽

Vol 2006 (04) ◽

pp. 594-596 ◽

Cited By ~ 3

Author(s):

Alessandra Silvani ◽

Giordano Lesma ◽

Alessandro Sacchetti

Keyword(s):

Carbon Monoxide ◽

Microwave Irradiation ◽

Palladium Catalyzed ◽

Vinyl Triflates

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ChemInform Abstract: In situ Generation of Carbon Monoxide from Solid Molybdenum Hexacarbonyl. A Convenient and Fast Route to Palladium-Catalyzed Carbonylation Reactions.

ChemInform ◽

10.1002/chin.200230108 ◽

2010 ◽

Vol 33 (30) ◽

pp. no-no

Author(s):

Nils-Fredrik K. Kaiser ◽

Anders Hallberg ◽

Mats Larhed

Keyword(s):

Carbon Monoxide ◽

Molybdenum Hexacarbonyl ◽

Fast Route ◽

Palladium Catalyzed ◽

In Situ Generation

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Synergistic Palladium-Phosphoric Acid Catalysis in (3 + 2) Cycloaddition Reactions between Vinylcyclopropanes and Imines

Catalysts ◽

10.3390/catal10020150 ◽

2020 ◽

Vol 10 (2) ◽

pp. 150 ◽

Cited By ~ 1

Author(s):

Vasco Corti ◽

Enrico Marcantonio ◽

Martina Mamone ◽

Alessandro Giungi ◽

Mariafrancesca Fochi ◽

...

Keyword(s):

Phosphoric Acid ◽

Palladium Catalyst ◽

Palladium Catalysts ◽

Acid Catalysis ◽

Cycloaddition Reaction ◽

Cross Coupling ◽

Cycloaddition Reactions ◽

Synergistic Catalysis ◽

Palladium Catalyzed ◽

First Time

The palladium-catalyzed (3 + 2) cycloaddition reaction between vinylcyclopropanes (VCPs) bearing geminal EWG’s and imines represents a straightforward and flexible entry to polysubstituted pyrrolidine derivatives. In this paper, we demonstrate that using a synergistic catalysis approach, based on the combination of phosphoric acid and palladium catalysts, it is possible to engage for the first time N-aryl and N-benzyl imines in this cycloaddition reaction. A range of polysubstituted pyrrolidines is obtained with moderate to good yields and diastereoselectivities, using a simple palladium species (Pd(PPh3)4) and an archetypical phosphoric acid as catalyst combination. A two-step scheme which exploits the same palladium catalyst for two consecutive and mechanistically distinct reactions (the cycloaddition and a Suzuki–Miyaura cross-coupling) is also presented. This synergistic catalysis approach is well posited for the development of the enantioselective version of this reaction. A screening of common BINOL-derived chiral phosphoric acids as catalyst component identified a species giving the product with moderate, yet promising, enantioselectivity (64% ee).

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Oxalic acid as the in situ carbon monoxide generator in palladium-catalyzed hydroxycarbonylation of arylhalides

Organic & Biomolecular Chemistry ◽

10.1039/c7ob01052d ◽

2017 ◽

Vol 15 (23) ◽

pp. 5033-5040 ◽

Cited By ~ 11

Author(s):

Changdong Shao ◽

Ailan Lu ◽

Xiaoling Wang ◽

Bo Zhou ◽

Xiaohong Guan ◽

...

Keyword(s):

Carbon Monoxide ◽

Oxalic Acid ◽

Highly Efficient ◽

Palladium Catalyzed

Oxalic acid as a highly efficient, safe and tractable concentrated carbon monoxide surrogate was successfully introduced into the palladium-catalyzed hydroxycarbonylation of arylhalides.

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