Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters

Yang, Ji; Liu, Jiawang; Ge, Yao; Huang, Wei-Heng; Ferretti, Francesco; Neumann, Helfried; Jiao, Haijun; Franke, Robert; Jackstell, Ralf; Beller, Matthias

doi:10.1002/anie.202015329

Cited by 36 publications

(12 citation statements)

References 53 publications

(15 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In previous work, we demonstrated the active participation of the ligand 1,2-bis(2-pyridyl( tert -butyl)phosphinomethyl)benzene ( L5 ) for the Pd-catalyzed alkoxy-/hydroxycarbonylations, whereby the 2-pyridyl group acts as a proton shuttle assisting in the metal hydride formation. − Inspired by this work, we envisioned that such a process might also promote amide hydrogenations. Indeed, the combination of Ru(acac) 3 (1 mol %), L5 (2 mol %), and KO t Bu (10 mol %) in THF was able to hydrogenatively cleave the C–N bond of benzanilide at 100 °C and under 30 bar of H 2 after 20 h, which led our further efforts dedicated to identifying other potential bidentate and monodentate phosphine ligands (Figure ).…”

Section: Resultsmentioning

confidence: 99%

Toward a Practical Catalyst for Convenient Deaminative Hydrogenation of Amides under Mild Conditions

Gausas

Jackstell

Skrydstrup

et al. 2022

ACS Sustainable Chem. Eng.

Self Cite

View full text Add to dashboard Cite

Amide bond reduction is a versatile transformation offering access to various alcohols and amines that could be used as valuable precursors in the chemical and pharmaceutical industries, e.g., for manufacturing plastics, textiles, dyes, agrochemicals, etc. Over the last two decades, catalytic amide hydrogenation employing homogeneous catalysis has gained more attention due to the atom efficiency and low environmental impact of this transformation. Owing to the inherent strength of amide bonds, amide hydrogenation procedures often involve high temperatures and pressures, which is why efforts are being channeled to finding protocols with lower-energy input. Here, we report a mild amide hydrogenation method involving commercially available precursors Ru(acac)3 and 1,2-bis(di-tert-butylphosphinomethyl)benzene (L4), which under basic conditions, at 80 °C and under 30 bar of H2, can selectively hydrogenate a series of 2°-benzamides to anilines and alcohols with yields of 36–98% and 29–92%, respectively. Additionally, 1°- and 3°-amides proved to be appropriate substrates; however, low to moderate yields were obtained. The catalyst is believed to operate via an inner-sphere mechanism with a hemiaminal being the likely intermediate during the hydrogenation process.

show abstract

Section: Resultsmentioning

confidence: 99%

Toward a Practical Catalyst for Convenient Deaminative Hydrogenation of Amides under Mild Conditions

Gausas

Jackstell

Skrydstrup

et al. 2022

ACS Sustainable Chem. Eng.

Self Cite

View full text Add to dashboard Cite

show abstract

“…As a last highlight, the reaction of diene ( 4sa ) solely yielded the branched product 4s in an 80% yield. This is remarkable as Pd or Ni typically gave the linear product …”

Section: Scope Evaluationmentioning

confidence: 90%

Asymmetric Addition of Allylsilanes to Aldehydes: A Cr/Photoredox Dual Catalytic Approach Complementing the Hosomi–Sakurai Reaction

et al. 2022

View full text Add to dashboard Cite

The allylation of aldehydes is a fundamental transformation in synthetic organic chemistry. Among the multitude of available reagents, allylsilanes especially have been established as a preferred allyl source. As initially reported by Hosomi and Sakurai, these non-toxic and highly stable reagents add to carbonyls via an open transition state upon Lewis acid activation. Herein, we report a general strategy to access a variety of valuable homoallylic alcohols in opposite chemo- and diastereoselectivity to the established Hosomi–Sakurai conditions by switching to photocatalytic activation in combination with a closed transition state (chromium catalysis). Moreover, this dual catalytic approach displays a straightforward way to introduce excellent levels of enantioselectivity and its mild conditions allow for a broad substrate scope including chiral boron-substituted products as a highlight. To emphasize the synthetic utility, our method was applied as the key step in the synthesis of a bioactive compound and in the late-stage functionalization of steroid derivatives. Detailed mechanistic studies and DFT calculations hint toward an unprecedented photo-initiated chain being operative.

show abstract

“…19 Besides, the commercial dtbpx was also effective in promoting such a transformation but partially lost time efficiency. 20 By contrast, the combination of palladium salts and monodentate phosphine ligands was widely employed in the carboxytelomerization of conjugated dienes with a specific ratio of dienes to alcohols. 21−23 We were recently interested in the regioselective functionalization of conjugated dienes and introduced a continuous process of the Pd-catalyzed methoxycarbonylation of 1,3butadiene.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Remarkably, the pyridyl-substituted bidentate phosphine ligand (HeMaRaphos) was recently developed to enable the direct transformation of conjugated dienes to linear diesters upon coordination with Pd(TFA) 2 . Besides, the commercial d t bpx was also effective in promoting such a transformation but partially lost time efficiency . By contrast, the combination of palladium salts and monodentate phosphine ligands was widely employed in the carboxytelomerization of conjugated dienes with a specific ratio of dienes to alcohols. − …”

Section: Introductionmentioning

confidence: 99%

Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes

Zhang

Han

et al. 2023

J. Org. Chem.

View full text Add to dashboard Cite

The Pd(cod)Cl2-catalyzed alkoxycarbonylation of conjugated dienes to β,γ-unsaturated esters was approached by both intramolecular phosphinesulfonate L1 and intermolecular PPh3/PTSA in this study. However, the poor solubility of the Pd/L1 complex and the labile monodentate Pd/PPh3 structure restricts the system efficiency, especially for the scale-up application. By contrast, the stable and well-soluble bidentate Xantphos system allows for the quantitative formation of 3-pentenoate (96%) on a gram scale within 6 h in weakly alkaline N-methylpyrrolidone (NMP), which also functions as a basic site to promote the rate-limiting alcoholysis step while reducing the dosage of ligand to a theoretical value.

show abstract

Efficient Palladium‐Catalyzed Carbonylation of 1,3‐Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters

Cited by 36 publications

References 53 publications

Toward a Practical Catalyst for Convenient Deaminative Hydrogenation of Amides under Mild Conditions

Toward a Practical Catalyst for Convenient Deaminative Hydrogenation of Amides under Mild Conditions

Asymmetric Addition of Allylsilanes to Aldehydes: A Cr/Photoredox Dual Catalytic Approach Complementing the Hosomi–Sakurai Reaction

Scalable Palladium-Catalyzed Alkoxycarbonylation of Conjugated Dienes

Contact Info

Product

Resources

About