Carbonylation of Enynes under Hydroformylation Conditions Catalyzed by Rhodium Carbonyl. A New Method for Synthesis of Cyclic Enones

Doyama, Kazuo; Joh, Takashi; Shiohara, T.; Takahashi, Shigetoshi

doi:10.1246/bcsj.61.4353

Cited by 44 publications

(14 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Besides the above-mentioned Pd-based protocols, methods involving other catalysts, including Co- [60] and Rh-based complexes [61][62][63][64][65][66]68,69,71,72,[75][76][77] , were reported to undergo hydroformylation of internal alkynes. However, the counterpart methods for terminal alkynes with adequate activity and chemoselectivity remain rather rare.…”

Section: Proposed Mechanismmentioning

confidence: 99%

“…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%

“…Therefore, many early protocols of hydroformylation of alkynes formed the target unsaturated aldehydes in low yields. During the past two decades, several methods of rhodium‐catalyzed hydroformylation of alkynes were reported, demonstrating that the selective production of α,β‐unsaturated aldehydes from alkynes is feasible [62–66,68,69,71,72,75–77,79] . Hereafter, only the palladium‐catalyzed hydroformylation of alkynes will be discussed.…”

Section: Pd‐catalyzed Hydroformylation Of Alkynesmentioning

confidence: 99%

“…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][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][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. One challenge that hinders the development of efficient hydroformylation protocols is the high reactivity of starting materials and products.…”

Section: Pd-catalyzed Hydroformylation Of Alkynesmentioning

confidence: 99%

See 3 more Smart Citations

Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

2021

View full text Add to dashboard Cite

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.

show abstract

Section: Proposed Mechanismmentioning

confidence: 99%

Section: Pd‐catalyzed Hydroformylation Of Alkynesmentioning

confidence: 99%

Section: Pd‐catalyzed Hydroformylation Of Alkynesmentioning

confidence: 99%

Section: Pd-catalyzed Hydroformylation Of Alkynesmentioning

confidence: 99%

See 2 more Smart Citations

Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

2021

View full text Add to dashboard Cite

show abstract

“…In 1990, Takahashi and co-workers found that the use of water instead of molecular hydrogen can give cyclocarbonylated products, 2(5H )-furanones, in excellent yield [12][13][14]. Later on, a novel rhodium-catalyzed carbonylation of [15].…”

mentioning

confidence: 99%

Rhodium-Catalyzed Carbonylative Synthesis of Heterocycles

Feng¹,

Wu²

2015

Topics in Heterocyclic Chemistry

View full text Add to dashboard Cite

show abstract

The Hydroformylation Reaction

et al. 2000

View full text Add to dashboard Cite

The reaction of 1‐alkenes with carbon monoxide and hydrogen in the presence of a catalyst gives the corresponding homologous aldehydes. The discovery of this reaction was made by Roelen in 1938 using Co 2 (CO) 8 as the catalyst at high temperature (120–170°) and high pressure of carbon monoxide/hydrogen (200–300 bar). This reaction has been called the “Oxo reaction”, “Roelen reaction” or “hydroformylation”. Hydroformylation is a general term indicating that both a hydrogen and a formyl group are introduced to unsaturated bonds, especially olefins. Later this reaction was developed as an industrial process, i.e., the Oxo Process, for the production of alkanals from 1‐alkenes using a cobalt or rhodium catalyst. Most noteworthy is the conversion of propene to butanal, which can be subsequently hydrogenated to 1‐butanol or converted to 2‐ethylhexanol by self‐aldol condensation. 2‐Ethylhexanol, a crucial intermediate for the production of ester‐type plasticizers, is the most important bulk chemical produced by the Oxo Process. A variety of transition metal catalysts other than Co 2 (CO) 8 have been investigated, including phosphine complexes of cobalt and hydridocobalt clusters. Platinum and ruthenium complexes show reasonably good catalytic activities, but modified cobalt catalysts are still much more advantageous. However, various rhodium complexes demonstrate higher catalytic activity (10 3 –10 4 times) than the cobalt complexes. Although the price of rhodium is higher than cobalt, reactions using rhodium catalysts require lower temperature (50–80°) and pressure (10–50 atm). Other important commercial applications of hydroformylation include the production of long‐chain alcohols from C 5 –C 17 isomeric linear alkenes. These long‐chain alcohols serve as intermediates for lubricants, plasticizers and detergents. The hydroformylation of ethene to propanal is another important Oxo Process. In this chapter, the authors put clear emphasis on the scope of the hydroformylation reaction in organic synthesis. In this context, there is a relevant review in 1987 of the hydroformylation of functionalized alkenes. The hydroformylation reaction now can be performed under very mild conditions using a variety of functionalized alkenes. Reactions in aqueous biphase, supercritical carbon dioxide or fluorous biphase have recently emerged in response to separation and environmental issues. In fact, a highly efficient Oxo Process using a water‐soluble rhodium catalyst in aqueous biphasic conditions has been commercialized by Ruhrchemie/Rhône‐Poulenc for the production of butanal. Asymmetric hydroformylation of prochiral olefins catalyzed by enantiopure rhodium complexes has been developed to the level that practical applications appear possible. Although the reactions of formaldehyde, oxiranes, and others with carbon monoxide and hydrogen in the presence of transition metal catalyst could be considered as variations of hydroformylation, this chapter only deals with hydroformylation of carbon‐carbon multiple bonds.

show abstract

Carbonylation of Enynes under Hydroformylation Conditions Catalyzed by Rhodium Carbonyl. A New Method for Synthesis of Cyclic Enones

Cited by 44 publications

References 19 publications

Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

Palladium‐Catalyzed Hydroformylation of Alkenes and Alkynes

Rhodium-Catalyzed Carbonylative Synthesis of Heterocycles

The Hydroformylation Reaction

Contact Info

Product

Resources

About