Palladium‐Catalyzed Cross‐Coupling of Furfuryl Alcohols with Arylboronic Acids <i>via</i> Aromatization‐Driven Carbon−Carbon Bond Cleavage to Synthesize 5‐Arylfurfuryl Alcohols and 2,5‐Diaryl Furans

Huang, Guanghao; Yin, Biaolin

doi:10.1002/adsc.201900799

Cited by 9 publications

(5 citation statements)

References 90 publications

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“…HMF has a primary hydroxyl group and a formyl group, as well as a furan ring, thus endowing this molecule with high chemical reactivity. It can be subjected to a multitude of chemical transformations such as oxidation, reduction, etherification, esterification, aldol condensation, and reductive amination, providing access to numerous useful chemicals such as 2,5-diformylfuran (DFF), 2,5-furandicarboxylic acid (FDCA), and 2,5-bis(hydroxymethyl)furan (BHMF). − BHMF, a symmetric and stable furan diol, is a versatile building block for the production of biobased polymers (e.g., polyesters, polyurethanes, and polyethers), − biofuels and fuel additives, − and valuable chemicals. , Its ester derivatives including monoesters and diesters have found applications as biodiesel additives, , flame retardants, plasticizers, and nonionic surfactants, as well as a selective protein acetylating agent …”

Section: Introductionmentioning

confidence: 99%

“…6−8 BHMF, a symmetric and stable furan diol, is a versatile building block for the production of biobased polymers (e.g., polyesters, polyurethanes, and polyethers), 9−12 biofuels and fuel additives, 13−15 and valuable chemicals. 16,17 Its ester derivatives including monoesters and diesters have found applications as biodiesel additives, 18,19 flame retardants, 20 plasticizers, 21 and nonionic surfactants, 22 as well as a selective protein acetylating agent. 23 In the past decades, significant advances in chemically catalytic conversion of HMF into BHMF were achieved; most routes were performed over metal-based catalysts, regardless of thermo-, electro-, and photocatalytic hydrogenation.…”

Section: ■ Introductionmentioning

confidence: 99%

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One-Pot Chemobiocatalytic Production of 2,5-Bis(hydroxymethyl)furan and Its Diester from Biomass in Aqueous Media

Qian

Zong

2023

ACS Catal.

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Direct valorization of biomass into value-added chemicals is attractive yet challenging. Herein, we report a one-pot synthesis of 2,5-bis(hydroxymethyl)furan (BHMF) and its diacetate from inexpensive fructose and sugar syrup in the aqueous phase via sequential chemical dehydration, biocatalytic reduction, and esterification. A robust alcohol dehydrogenase from Escherichia coli (EcYjgB) was identified for HMF reduction, with high catalytic efficiencies toward 5hydroxymethylfurfural (HMF) (k cat /K m , 1300 s −1 mM −1 ) as well as NADPH (9700 s −1 mM −1 ). Recombinant E. coli harboring EcYjgB (E. coli_EcYjgB) showed high tolerance toward highly toxic and strongly inhibitory biobased furans, enabling smooth reduction of 1 M HMF and 0.5 M furfural. Its practicality was demonstrated by gram-scale synthesis of BHMF with a 79% isolated yield at approximately 126 g/L substrate loading. Biocatalytic process intensification was realized by improving cell membrane permeability using ethyl acetate, providing up to 15 g/L h BHMF productivity. A concurrent biocatalytic cascade for producing BHMF diacetate from HMF was constructed by combining E. coli_EcYjgB and Mycobacterium smegmatis acyltransferase (MsAcT) variant N94A, affording the desired product with a 93% yield in 1 h. Starting from crude HMF obtained via chemical dehydration and organic solvent evaporation, BHMF and its diacetate were produced with >99 and 88% yields, respectively. Finally, direct synthesis of these furan-based products from sugars was performed by chemobiocatalysis, without isolation of any intermediates, resulting in yields of up to 59% (relative to sugar). This work may pave the way for scalable production of furan-based chemicals from inexpensive renewable biomass.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

One-Pot Chemobiocatalytic Production of 2,5-Bis(hydroxymethyl)furan and Its Diester from Biomass in Aqueous Media

Qian

Zong

2023

ACS Catal.

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“…A relatively small electronic effect from the β-aryl substituent of the enone substrate suggests of a metal-mediated nonelectrophilic C–C cleavage process. Similar moderate electronic effect with a relatively low Hammett ρ value has been observed for metal-mediated nonelectrophilic cleavage reactions of C–H, C–C and C–Si bonds …”

Section: Resultsmentioning

confidence: 96%

Catalytic Carbon–Carbon Bond Activation of Saturated and Unsaturated Carbonyl Compounds via Chelate-Assisted Coupling Reaction with Indoles

Pannilawithana

2020

ACS Catal.

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The chelate assistance strategy was devised to promote a highly regioselective catalytic C–C bond activation reaction of saturated and unsaturated carbonyl compounds. The cationic Ru–H complex 1 was found to be an effective catalyst for mediating the coupling reaction of 1,2-disubstituted indoles with α,β-unsaturated aldehydes and ketones, in which the regioselective Cα–Cβ activation of the carbonyl substrates has been achieved in forming the 3-alkylindole products. The analogous coupling reaction of indoles with saturated aldehydes and ketones directly led to the Cα–Cβ cleavage of the carbonyl substrates in forming the 3-alkylindole products. The coupling reaction of 1,2-dimethylinole with (E)-3-nonen-2-one and 2-propanol-d 8 showed 20–22% of deuterium incorporation to both α- and β-CH2 of the 3-alkylindole product. The coupling reaction of 1,2-dimethylinole with (E)-3-nonen-2-one exhibited the most significant carbon kinetic isotope effect on the α-carbon of the product (Cα = 1.046). The Hammett plot constructed from the reaction of 1,2-dimethylinole with a series of para-substituted enones p-X-C6H4CHCHCOCH3 (X = OMe, Me, H, Cl, CF3) showed a modest promotional effect by an electron-donating group (ρ = −0.2 ± 0.1). Several catalytically relevant Ru–H species were detected by NMR from a stoichiometric reaction mixture of the Ru–H complex 1 with 1,2-dimethylindole and (E)-3-nonen-2-one in CD2Cl2. These results support a mechanism of the catalytic coupling reaction via conjugate addition of indoles to enones followed by the C–C bond activation and hydrogenolysis steps.

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“…The same group expanded the scope of the reaction to monoprotected furfuryl diols 331 using slightly modified conditions (Scheme 53). 116 To confirm the mechanistic hypothesis that the mechanism proceeds via an oxonium ion and not via β-carbon elimination, the authors conducted a Hammett study. The large negative ρ value of −0.56, together with the inverse reactivity trend of substitution of the alcohol supported the mechanism proposed above (Scheme 52).…”

Section: β-Alkyl Elimination With Rhodiummentioning

confidence: 99%

Metal-Catalyzed Carbon–Carbon Bond Cleavage of Unstrained Alcohols

2020

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The functionalization of molecules by cleaving inert carbon–carbon single bonds is regarded as a great synthetic challenge due to their inherent stability. In recent years, significant progress has been made in the activation of small rings relying on the release of strain energy. By contrast, the number of catalytic methodologies for the activation of unstrained carbon–carbon single bonds is still limited. This review focuses on the recent developments in transition-metal-catalyzed cleavage of C–C bonds in unstrained alcohols via β-carbon elimination. Emphasis is placed on the mechanistic aspects of the discussed transformations and their applications to the deconstruction and reorganization of molecules.

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Palladium‐Catalyzed Cross‐Coupling of Furfuryl Alcohols with Arylboronic Acids via Aromatization‐Driven Carbon−Carbon Bond Cleavage to Synthesize 5‐Arylfurfuryl Alcohols and 2,5‐Diaryl Furans

Cited by 9 publications

References 90 publications

One-Pot Chemobiocatalytic Production of 2,5-Bis(hydroxymethyl)furan and Its Diester from Biomass in Aqueous Media

One-Pot Chemobiocatalytic Production of 2,5-Bis(hydroxymethyl)furan and Its Diester from Biomass in Aqueous Media

Catalytic Carbon–Carbon Bond Activation of Saturated and Unsaturated Carbonyl Compounds via Chelate-Assisted Coupling Reaction with Indoles

Metal-Catalyzed Carbon–Carbon Bond Cleavage of Unstrained Alcohols

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