Regioselective Hydroformylation of Enynes Catalyzed by a Zwitterionic Rhodium Complex and Triphenyl Phosphite

and, Bernard G. Van den Hoven; Alper, Howard

doi:10.1021/jo982425y

Cited by 65 publications

(22 citation statements)

References 23 publications

(21 reference statements)

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“…In contrast to the transition‐metal‐catalyzed hydroformylation of olefins, which is among the most extensively studied catalytic reactions, hydroformylation of alkynes gained rather limited attention over the years [60–78] . This disparity might be surprising, considering that the products, the α,β‐unsaturated aldehydes are important intermediates in organic synthesis, particularly for the synthesis of bioactive compounds, flavors, and fragrances.…”

Section: Pd‐catalyzed Hydroformylation Of Alkynesmentioning

confidence: 99%

Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

2021

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Dedicated to Prof. Eite Drent for his contributions to the field of Pd-catalyzed hydrocarbonylation chemistryHydroformylation of alkenes and alkynes with syngas represents a method of choice to furnish valuable aldehydes with the 100 % atom-economy from readily available building blocks. The field is dominated by Rh-and Co-catalysis; however, complexes of many other metals were also shown to be catalytically competent. Here we review the studies of hydroformylation under Pd-catalysis, starting from the seminal reports up to the most recent examples. Special emphasis is paid to the unique regio-and chemoselectivities of Pd-based methods, which are difficult to achieve with the conventional hydroformylation protocols. Different mechanistic proposals are presented along with a summary of their experimental and computational support. Finally, the user-friendly methods using surrogates of syngas are discussed as well. Overall, the Minireview aims to present unique opportunities and remaining challenges of Pd-catalyzed hydroformylation reactions for their prospective applications in fine-chemical synthesis.

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Section: Pd‐catalyzed Hydroformylation Of Alkynesmentioning

confidence: 99%

Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

2021

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“…The early studies10–16 found that alkynes hydroformylation usually suffered from the low selectivity and/or low yield of unsaturated aldehydes. Fortunately, during the latest two decades, several effective catalysts such as the catalyst system of [Rh(CO) 2 (acac)] and a sophisticated bisphosphite ligand,17 the heterobimetallic catalyst [PdCl 2 (PCy 3 ) 2 ]/[Co 2 (CO) 8 ],18 and the zwitterionic rhodium complex with triphenyl phosphite as ligand19, 20 were developed. These exciting achievements revealed that the hydroformylation of acetylenic species to α,β‐unsaturated aldehydes with high activity and selectivity is accessible.…”

Section: Introductionmentioning

confidence: 99%

Hydroformylation and Isomerization of Allene and Propyne: A Density Functional Theory Study

Huo¹,

Li²,

Beller³

et al. 2005

Chemistry A European J

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The [HCo(CO)3]-catalyzed hydroformylation of allene and propyne has been investigated at the B3LYP level of density functional theory. It is found that hydroformylation of allene favors the linear anti-Markovnikov product in high regioselectivity both kinetically and thermodynamically. The origin of this regioselectivity comes from the enhanced stability of the eta3-allylic intermediate [(eta3-CH2CHCH2)Co(CO)3]. By contrast, propyne does not show any regioselectivity. The possible interconversion between allene and propyne mediated by [HCo(CO)3] has been explored.

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“…[1] Among various synthetic approaches to a,bunsaturated aldehydes,t he hydroformylation of alkynes is generally regarded as one of the most efficient and rapid methods and has been of great interest to synthetic chemists. [2] Over the past few decades,alot of catalytic systems have been reported, as exemplified by the pioneering works of the Buchwald, [3] Hidai, [4] Alper, [5] Beller, [6] Breit, [7] and Zhang [8] groups,a ll of which focus on the conversion of alkynes,C O, and H 2 into aldehydes (Scheme 1a). Despite strenuous effort, two fundamental issues remain for the further application of the hydroformylation reaction.…”

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confidence: 99%

Syngas‐Free Highly Regioselective Rhodium‐Catalyzed Transfer Hydroformylation of Alkynes to α,β‐Unsaturated Aldehydes

Tan

Shi

et al. 2019

Angew Chem Int Ed

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The hydroformylation of alkynes is af undamental and important reaction in both academic researcha nd industry.C onventional methods focus on the conversion of alkynes,C O, and H 2 into a,b-unsaturated aldehydes,b ut they often suffer from problems associated with operation, regioselectivity,and chemoselectivity.Herein, we disclose an operationally simple,m ild, and syngas-free rhodium-catalyzed reaction for the hydroformylation of alkynes via formyl and hydride transfer from an alkyl aldehyde.This synthetic method uses inexpensive and easy-to-handle n-butyraldehyde to overcome the challenge posed by the use of syngas in traditional approaches and employs acommercially available catalyst and ligand to transform ab road range of internal alkynes, especially alkynyl-containing complex molecules,into versatile stereodefined a,b-unsaturated aldehydes with excellent chemo-,regio-, and stereoselectivity. Scheme 1. Hydroformylation of alkynes to a,b-unsaturated aldehydes.

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Regioselective Hydroformylation of Enynes Catalyzed by a Zwitterionic Rhodium Complex and Triphenyl Phosphite

Cited by 65 publications

References 23 publications

Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

Hydroformylation and Isomerization of Allene and Propyne: A Density Functional Theory Study

Syngas‐Free Highly Regioselective Rhodium‐Catalyzed Transfer Hydroformylation of Alkynes to α,β‐Unsaturated Aldehydes

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