Highly selective hydroformylation of 3,3,3-trifluoropropene to 4,4,4-trifluorobutanal using Rh/Xantphos catalyst

Ohtsuka, Yoshihiro; Kobayashi, Osamu; Yamakawa, Tetsu

doi:10.1016/j.jfluchem.2014.02.005

Cited by 8 publications

(5 citation statements)

References 23 publications

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“…This was achieved using an oxime and oxidizing agent PhI(OAc) 2 , to produce heterocycle 11 in 81 % yield. Finally, using conditions optimized for trifluoropropene, a hydroformylation reaction was utilized to convert alkene 6 b to aldehyde 12 .…”

Section: Figurementioning

confidence: 99%

Synthesis of Diverse α‐Fluoroalkoxyaryl Derivatives and Their Use for the Generation of Fluorinated Macrocycles

Cogswell

Dahlén

Knerr

2018

Chemistry A European J

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Introduction of difluorinated functionality has emerged as ap owerful meansf or conformational design with minimal steric footprint. Synthetic approaches for the preparation of aryl difluoromethylene etherc ontaining novel buildingblocks wereestablished, enabling the inclusion of the aryl difluoromethylene ether systemi nto macrocyclics caffoldsfor the first time.The rational introductiono ff luorine atoms has becomeakey tool for organic chemists to modulate not only the physicochemicalb ut also the conformational properties of am olecule. With the tremendous progress made to extend the variety of synthetic fluorination methods [1] available,i ti sn os urprise to see the increasing impact of fluorination in contemporary catalysis, [2] pharmaceutical, [3] and agrochemical [4] design. Among the properties of the CÀFb ond, [5] its capacityt oe ngage in charge-dipole interactions, dipole-dipole interactions, as well as hyperconjugation have all been exploited to fine-tune the conformation of aw ide range of biomolecules including fatty acids, [6] alpha, [7] beta, [8] and gamma [9] amino acids and their oligomers. Some of these approaches have recently been applied to the modulation of the conformation of macrocyclic scaffolds.O 'Hagan and co-workers have, for example, probed

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Section: Figurementioning

confidence: 99%

Synthesis of Diverse α‐Fluoroalkoxyaryl Derivatives and Their Use for the Generation of Fluorinated Macrocycles

Cogswell

Dahlén

Knerr

2018

Chemistry A European J

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“…In 2014 Yamakawa and co-workers developed the synthesis of the linear isomer (12) using milder conditions (Scheme 19C). 80 Utilization of a rhodium complex and XantPhos ligand, the linear aldehyde was isolated in 80% yield under 1 atm pressure of CO/H2 mixture after 2 hours. Later the branched isomer was produced in a stereoselective manner as well.…”

Section: Hydroesterification Hydroformylationmentioning

confidence: 99%

“…In 2014, Yamakawa and co-workers reported the synthesis of the linear isomer 122 using milder conditions (Scheme 19C). 80 Utilizing of a rhodium complex and Xantphos ligand gave the linear aldehyde 122 in 80% yield under 1 atm pressure of CO/H 2 mixture after 2 h. In 2003, Shibahara, Nozaki, and Hiyama reported the production of the branched isomer 123 in a stereoselective manner (Scheme 19D). 81 Effective gas mixing of CO/H 2 (syngas) and 3,3,3-trifluoroprop-1-ene (1) in an autoclave, followed by passing the mixture through a column packed with modified silica gel prepared with the rhodium complex of the chiral (R,S)-BINAPHOS gave branched aldehyde 123 with 95% selectivity with 93% ee.…”

Section: Short Review Synthesismentioning

confidence: 99%

Application of Industrially Relevant HydroFluoroOlefin (HFO) Gases in Organic Syntheses

et al. 2021

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Hydrofluoroolefin (HFO) gases are state-of-the-art cooling agents with widespread household and industrial applications. Considering their structural benefits these fluorous feedstocks gained attention of organic chemists in the last couple of years. In this short review we summarized the existing synthetic transformations of these gaseous starting material and present their applicability in the synthesis of fluorine containing organic molecules, which have potential importance as building blocks and reagents for diverse syntheses.

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“…[4][5][6][7][8] Furthermore, ruthenium(0) complexes with triphenylphosphine such as Ru(CO) 3 (PPh 3 ) 2 , RuH 2 (CO) 2 (PPh 3 ) 2 and others have been efficient catalysts in the hydroformylation of olefins. [9][10][11] On the other hand, Ru(II) complexes like dichlorotris(triphenylphosphine)ruthenium(II), and RuCl 2 (PPh 3 ) 3 have been found to be effective catalysts in the hydroformylation of propen-1-ol.…”

Section: Introductionmentioning

confidence: 99%

MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE

Moya

Yáñez-S

Pérez

et al. 2016

J. Chil. Chem. Soc.

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The catalytic activity of systems of type [RuH(CO)(N-N)(PR 3 ) 2 ] + was evaluated in the hydroformylation reaction of 1-hexene. The observed activity is explained through a reaction mechanism on the basis of the quantum theory. The mechanism included total energy calculations for each of the intermediaries of the elemental steps considered in the catalytic cycle. The deactivation of the catalyst precursors takes place via dissociation of the polypyridine ligand and the subsequent formation of thermodynamically stable species, such as RuH(CO) 3 (PPh 3 ) 2 and RuH 3 (CO)(PPh 3 ) 2 , which interrupt the catalytic cycle. In addition, the theoretical study allows to explain the observed regioselectivity which is defined in two steps: (a) the hydride migration reaction with an anti-Markovnikov orientation to produce the alkyl-linear-complex (3.1a), which is more stable by 19.4 kJ/mol than the Markovnikov orientation (alkyl-branched-complex) (3.1b); (b) the carbon monoxide insertion step generates the carbonyl alkyl-linear specie (4.1a) which is more stable by 9.5 kJ/mol than the alternative species (4.1b), determining the preferred formation of heptanal in the hydroformylation of 1-hexene.

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Highly selective hydroformylation of 3,3,3-trifluoropropene to 4,4,4-trifluorobutanal using Rh/Xantphos catalyst

Cited by 8 publications

References 23 publications

Synthesis of Diverse α‐Fluoroalkoxyaryl Derivatives and Their Use for the Generation of Fluorinated Macrocycles

Synthesis of Diverse α‐Fluoroalkoxyaryl Derivatives and Their Use for the Generation of Fluorinated Macrocycles

Application of Industrially Relevant HydroFluoroOlefin (HFO) Gases in Organic Syntheses

MECHANISTIC STUDY OF A RUTHENIUM HYDRIDE COMPLEX OF TYPE [RuH(CO)(N-N)(PR3)2]+ AS CATALYST PRECURSOR FOR THE HYDROFORMYLATION REACTION OF 1-HEXENE

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