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Synthesis 2024; 56(11): 1807-1814
DOI: 10.1055/a-2241-6966
paper

Zinc/Bismuth-Mediated Allylation Reaction of Biomass Feedstocks: Synthesis of Furanic Diols

Soumen Biswas
,
Prakash Kannaboina
,
Mukund P. Sibi  ∗

We thank the U.S. Army Research Laboratory for funding under cooperative agreement W911-NF-19-2-0138.
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This paper is dedicated to Prof. Dennis Curran on the occasion of his 70th birthday.

Abstract

Biomass-based diols have been synthesized by a Zn/Bi-mediated Barbier-type of reaction from furanic aldehydes and allyl halides to access allylated diols. The allylated diols can be readily converted into alkylated diols by hydrogenation. These furanic diols could be potential replacements for fossil fuel based bisphenol A (BPA) which has an adverse endocrine-disrupting effect on humans. This mild and green protocol provides symmetric and nonsymmetric diols in high yields. A chemoselective reduction of allylic double bonds provides diols with unique substitution.


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Key words

bisphenol A - furanic diols - Barbier reaction - biomass - allylation - zinc - bismuth

The search for alternative energy and chemical sources has received a lot of attention in recent decades, due to the rapid depletion of fossil resources. Fossil fuels are important in the energy industry and they are also the primary carbon source in the chemical industry. Different types of biomass have been investigated as an alternative to fossil fuels for energy production.[1] Furthermore, biomass is an important carbon source in the production of chemicals.[2] As a result, research into alternate strategies for harvesting chemicals and biofuels from sustainable biomass has gained a lot more attention than before.[3]

Fossil fuel derivative bisphenol A (BPA) (Scheme [1]A) is well known for its broad use in the consumer industry for manufacturing polycarbonates that are used in reusable plastic bottles. Moreover, BPA-derived epoxy resins are used in electronics, adhesives, container coatings, etc.[4] Recent biological studies have indicated several health hazards that are associated with the excessive use of BPA including reproductive toxicity and endocrine-disrupting properties.[5] Although many BPA replacements have been used by the chemical industry, most of them are derived from fossil fuels.[6] In a previous report, we found diols synthesized from biomass feedstock 5-hydroxymethylfurfural (HMF) and its congeners could be potential candidates to replace BPA since some of these diols (Scheme [1]B) exhibited no endocrine activity while others showed diminished activity when compared to BPA.[7] Additionally, several of the newly synthesized diols showed low toxicity.

Zoom Image
Scheme 1 Synthesis of biomass-based diols

Our reported synthesis of biobased furanic diols was carried out by the addition of a Grignard reagent to HMF and its congeners (Scheme [1]C). This protocol has several shortcomings: (1) Grignard reagents are water-reactive and pyrophoric, (2) the reaction requires inert conditions, (3) the need for anhydrous solvents, (4) greater than 2 equivalents of the Grignard reagent is required when working with HMF (1 equivalent deprotonates the hydroxyl group), (5) cost, (6) selective monoalkylation of dialdehydes, and (7) difficulty of scale-up in an academic setting. In contrast, allylic halides are known to undergo a Barbier-type of reaction with aldehydes in the presence of different metals under mild conditions to provide allylic alcohols in high yields.[8] Especially, zinc-,[9] indium-,[10] iron-,[11] and bismuth-derived[12] allylmetal halides have been investigated extensively for reactions with aldehydes, giving rise to allyl-substituted alcohol derivatives. Recently, allylations of aldehydes using ball milling and photoredox chemistry using Zn or Bi have been reported.[13] A few greener approaches using water as a solvent have also been reported.[8`] [d] [e] [f]

Selective monoallylation/alkylation of dialdehydes is quite challenging. Selective monoallylation will allow for further diversified products, especially in the formation of unsymmetrical diols. Thus, development of a user-friendly, inexpensive, selective, and high-yielding green method for the synthesis of biobased diols is warranted.

Table 1 Optimization of the Allylation Reaction with Zinca

Entry

Conditionsa

Time

2 (equiv)

Yield (%)b 3

1

Zn (1.0 equiv), THF–NH4Cl (2:1)

 1 h

3

53

2

Zn (1.5 equiv), THF–NH4Cl (2:1)

30 min

2.5

75

3

Zn (2.0 equiv), THF–NH4Cl (2:1)

 5 min

2

80

4

Zn (3.0 equiv), THF–NH4Cl (2:1)

 5 min

2

72

5

Zn (2.0 equiv), NH4I (2.0 equiv), THF–H2O (2:1)

20 min

2

42

6

Zn (2.0 equiv), THF–H2O (2:1)

12 h

2

n.r.

7

Zn (2.0 equiv), DMF–NH4Cl (2:1)

 2 h

2

50

a Reaction conditions: 1 (1.0 mmol), 2, solvent (0.5 M), rt; saturated NH4Cl solution, Zn (100 mesh, 99.0%, activated with 2 M HCl).

b Isolated yield after purification; n.r. = no reaction.

Bismuth and zinc have a unique functional group tolerance and muted reactivity towards aldehydes when compared to Grignard reagents.[10] [14] Especially, organobismuth reagents from allyl halides are well known for their mild reactivity, low toxicity, and excellent chemoselectivity. Hence, we realized a mild, relatively green, and high-yielding method using Bi or Zn may be achievable. In this manuscript, we report a mild and green protocol to synthesize symmetric and unsymmetric furanic diols from biomass derivatives HMF and diformylfuran (DFF) under aqueous conditions by using inexpensive and easy-to-handle Zn dust or Bi metal. The alkylated derivatives of the diols can be synthesized by Pd/C-mediated alkene reduction (Scheme [1]D).

We started our investigation using HMF (1) and allyl bromide (2) in the presence of Zn and THF–NH4Cl solvent mixture which provided the corresponding allyl-substituted furyl diol 3 in 53% yield (Table [1], entry 1). In order to enhance the yield of the desired product 3, the loading of Zn was increased up to 3.0 equivalents (Table [1], entries 2–4). It was observed that 2.0 equivalents of Zn gave the best yield of 80% (Table [1], entry 3). Ammonium iodide when used as an additive under similar conditions gave an inferior yield (42%) of 3 (Table [1], entry 5). Notably, it was observed that the reaction was unsuccessful in the absence of ammonium salt (Table [1], entry 6). A change in solvent combination (DMF–NH4Cl) also did not improve the yield. Hence, the optimal conditions were as described in entry 3 and were applied to explore the substrate scope for the reaction, with the results summarized in Scheme [2].

Several substituted allyl bromides reacted with HMF (1), leading to the corresponding diols 11–17 (Scheme [2]) in good to excellent yields (63–90%). It is interesting to note that a substituted allyl bromide such as crotyl bromide gave a mixture of inseparable diastereomeric diols 11 with moderate diastereoselectivity (dr = 80:20) and good yield (75%). Allyl bromide with an electron-withdrawing ester functionality furnished product 15 in high yield (90%). The reaction conditions are also compatible with less reactive propargyl bromide that produced compound 17 in moderate yield (63%). The allylation reaction was scaled up to 200.0 mmol and the desired product 3 was obtained in comparable yield (75%).

Zoom Image
Scheme 2 Zn-mediated allylation reaction with HMF (1)

In a similar manner, the optimized reaction protocol was applied to the dialdehyde DFF (18) to synthesize the respective furyl diols (Scheme [3]). It was noticed that all the furyl diols 19–24 were obtained in excellent yields (75–85%). Moreover, some other allyl-substituted biomass derivatives 25–28 were also synthesized, demonstrating the broad substrate scope for the methodology. The syntheses of starting materials for 27 and 28 are provided in the Supporting Information.

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Scheme 3 Zn-mediated allylation reaction with DFF (18)

The allylation of HMF was further investigated using less reactive bismuth. The initial trial reaction was performed using HMF (1) and allyl bromide (2, 1.5 equiv) in the presence of Bi and DMF–H2O solvent mixture which provided the corresponding allyl-substituted furyl diol 3 in 76% yield (Table [2], entry 1). When the amount of allyl bromide was increased to 2.0 equivalents, a slightly better yield of 77% for the diol 3 was realized (Table [2], entry 2). The reaction was also performed in different solvent mixtures, such as THF–H2O, 2-MeTHF–H2O, and cyclopentyl methyl ether (CPME)–H2O, and they produced the desired product in inferior yields (Table [2], entries 3–5). Use of BiCl3 in the presence of a reducing metal (Zn or Fe) failed to enhance the yield (Table [2], entries 6 and 7). Notably, it was observed that the presence of ammonium iodide as an additive was critical to the success of the reaction (Table [2], entry 8). Reported Bi-mediated Barbier-type allylation of aldehydes involves the use of a solventless ball milling technique that requires up to 8.0 equivalents of Bi with respect to the carbonyl compounds used.[15] Bi-mediated aqueous Barbier-type allylations require bismuth salts and reducing metal[16] or additives such as fluoride ions.[17]

Table 2 Optimization of the Reaction Conditions with Bismutha

Entry

Conditionsa

Time (h)

2 (equiv)

Yield (%)b 3

1

Bi (1.5 equiv), NH4I (1.5 equiv), DMF–H2O (2:1)

 3

1.5

76

2

Bi (1.5 equiv), NH4I (1.5 equiv), DMF–H2O (2:1)

 3

2

77

3

Bi (1.5 equiv), NH4I (1.5 equiv), THF–H2O (2:1)

 6

2

60

4

Bi (1.5 equiv), NH4I (1.5 equiv), 2-MeTHF–H2O (2:1)

 6

2

68

5

Bi (1.5 equiv), NH4I (1.5 equiv), CPME–H2O (2:1)

10

2

45

6

BiCl3 (1.5 equiv), Zn (2.0 equiv), THF

12

2

56

7

BiCl3 (1.5 equiv), Fe (2.0 equiv), THF

12

2

65

8

Bi (1.5 equiv), DMF

12

2

n.r.

a Reaction conditions: 1 (1.0 mmol), 2, solvent (0.5 M), rt; saturated NH4I solution.

b Isolated yield; n.r. = no reaction.

We also investigated the selectivity of the Bi-mediated Barbier reaction towards monoallylation reaction. To ascertain the feasibility of monoallylation, we investigated the reaction of allylmetal reagents with DFF (18). It was observed that very reactive ethylmagnesium bromide (1.0 equiv) on reaction with DFF (18) provided a mixture of starting material and mono- and disubstituted products in 1:2.1:3 ratio (Scheme [4]).

Zoom Image
Scheme 4 Grignard reaction with DFF (18)

Similarly, reaction with Zn/allyl halide was also unsuccessful in generating monoallyl-substituted product solely (mixture of mono- and disubstituted product and starting material is formed; results not shown here). Hence, we envisioned that another metal with milder reactivity, such as bismuth, could be used for selective monoallylation. To our delight, when allyl bromide and DFF (18) were combined in 1:1 molar ratio in the presence of Bi and NH4I in DMF–H2O solvent mixture, the monoallylated product 31 was obtained exclusively in 81% yield (Scheme [5]). Similar reaction conditions were used for different substituted allyl bromides, such as crotyl bromide, 3,3-dimethylallyl bromide, 2-methylallyl bromide, methyl 2-(bromomethyl)acrylate, and 3-bromocyclohexene; to our delight, it was observed that solely monosubstituted products 32–36 were obtained in moderate to very good yields (68–80%). Similar Bi-mediated Barbier-type reactions undergo α-substitution as opposed to γ-substitution (reported here for 32 and 33).[18] [19] To our knowledge, such monoallylations of dialdehydes are not known.

Zoom Image
Scheme 5 Bi-mediated monoallylation reaction with DFF (18)

This interesting result motivated us to apply the protocol to aryl dicarboxaldehydes to synthesize the corresponding monoallylated derivatives. Hence, terephthaldehyde and isophthaldehyde were treated separately under the developed conditions with bismuth and 1 equivalent of allyl bromide. Interestingly, the corresponding monoallyl-substituted derivatives 38 and 39 were formed in very good yields (82–84%) (Scheme [6]). In contrast, aliphatic dicarboxaldehydes such as cyclohexane-1,4-dicarboxaldehyde failed to generate allylated alcohols under similar conditions. Nevertheless, aliphatic dicarboxaldehydes like cyclohexane-1,4-dicarboxaldehyde and cyclopentane-1,3-dicarboxaldehyde underwent Zn-mediated diallylation reaction, providing the corresponding products 41 and 43 in very good yields (80–85%).

Zoom Image
Scheme 6 Selective allylation reactions with other aromatic dialdehydes

We anticipated that monoallylated DFF derivative 31 containing an aldehyde group could be treated with substituted allyl bromides for the synthesis of unsymmetrically substituted allylated diol derivatives. Therefore, 5-(1-hydroxybut-3-en-1-yl)furan-2-carboxaldehyde (31) was combined with crotyl bromide and other allylating reagents using Zn, THF-NH4Cl to synthesize the corresponding unsymmetrically substituted furyl diols 44–48 in good yields (74–84%) (Scheme [7]). Furthermore, we were able to synthesize unsymmetrically substituted derivative 44 in one pot by sequential addition of allyl bromide followed by addition of crotyl bromide, in comparable yield (79%).

Zoom Image
Scheme 7 Unsymmetrical allylation from monoallyl-substituted DFF derivative 31

One of the drawbacks to Barbier-type transformations is that only reactive halides can be used in the reactions, thus limiting access to saturated alkyl substituents in the products. One way to overcome this deficiency is the ability to convert the allylated products into saturated ones by reduction. To evaluate such a methodology, the allylic double bond of compound 3 was subjected to reduction using hydrogen and a catalytic amount of Pd/C. This reaction cleanly delivered propyl-substituted HMF derivative 49 in excellent yield (87%). Further, this catalytic hydrogenation was applied to other allylic HMF/DFF-based diols (27, 16, 19) to furnish the corresponding alkyl-substituted HMF- and DFF-based diols 50, 51, and 52, respectively, in good to excellent yields (75–87%) (Scheme [8]).

Zoom Image
Scheme 8 Hydrogenation of allylation derivatives

We were also interested in examining chemoselective reduction of unsymmetrical allyl-substituted diols to access structurally diverse compounds (Scheme [9]). To our delight, when compound 47 was subjected to reduction using Pd/C, the electron-rich double bond was reduced and the corresponding alkyl-substituted diol 53 was obtained in very good yield (82%). In contrast, when compound 47 was treated with NiCl2/NaBH4, the electron-deficient double bond was reduced selectively and in situ cyclization led to formation of furyl derivative 54 substituted with a five-membered lactone, in excellent yield (92%).

Zoom Image
Scheme 9 Chemoselective hydrogenation

In summary, we have developed a simple, mild, and green protocol for the synthesis of various allyl-substituted diols from readily available biomass-derived feedstocks such as hydroxymethylfurfural (HMF), 2,5-furandicarboxaldehyde (DFF), and related furfural derivatives. With dialdehydes, the Zn-mediated protocol provides disubstituted furanic diols whereas more selective Bi gives monoallyl-substituted products. Moreover, we have been able to access unsymmetrical allyl-substituted furanic diols through this protocol. Furthermore, the allylic double bonds can be reduced successfully to obtain alkyl-substituted diols in very good yields. A chemoselective reduction methodology is also reported for unsymmetrical allylated diol to access a unique class of biomass-derived scaffolds.

Unless otherwise stated, all commercially procured materials were used as received without further purification. Furanic compounds were synthesized using biobased HMF from Avantium. DFF was synthesized from HMF by MnO2 oxidation in dichloromethane. All other compounds that were not synthesized in-house were from Sigma-Aldrich. NMR spectra were recorded on a Bruker Avance 400 MHz instrument and processed with TopSpin software. IR spectra were recorded with a Nicolet™ iS™ 10 Fourier transform infrared spectrometer using a diamond sample plate for attenuated total reflectance. High-resolution mass spectra were recorded on a Waters Synapt G2-Si high-definition mass spectrometer and were processed using MassLynx. Unless otherwise stated, all reactions were stirred magnetically by polytetrafluoroethylene-coated magnetic spin bars. All mention of silica gel refers to Sorbtech standard grade silica gel, 230–400 mesh.


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Synthesis of Allyl-Substituted HMF Derivatives (Using Zn); General Procedure 1

HMF (126.0 mg, 1.0 mmol) was dissolved in THF (1.0 mL) in a vial. Saturated NH4Cl solution (0.5 mL) was added to the vial. Activated Zn (130.8 mg, 2.0 mmol) was added to this reaction mixture and the heterogeneous mixture was stirred vigorously. Allyl bromide (1.5 mmol) was added dropwise. After completion of the reaction (monitored by TLC), the reaction mixture was diluted with ethyl acetate (6.0 mL) and sodium sulfate was added. The ethyl acetate layer was filtered through Celite and the filtrate was concentrated by rotary evaporator to obtain the crude product. The crude material was purified by silica gel flash chromatography (ethyl acetate–hexane, 1:3 to 1:2) and the pure product was obtained generally as a colorless oil.


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1-(5-(Hydroxymethyl)furan-2-yl)but-3-en-1-ol (3)

Colorless oil; yield: 80%; following procedure 1.

FTIR (neat): 3315, 2922, 1642, 1416, 1363, 1313, 1183, 1007, 917, 793 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.16–6.12 (m, 2 H), 5.77 (ddt, J = 18.0, 11.0, 7.0 Hz, 1 H), 5.14–5.07 (m, 2 H), 4.63 (t, J = 8.0 Hz, 1 H), 4.46 (s, 2 H), 3.34 (br s, 2 H), 2.60–2.52 (m, 2 H).

13C NMR (100 MHz, CDCl3): δ = 156.0, 153.5, 133.9, 118.3, 108.4, 106.9, 66.9, 57.1, 39.8.

HRMS (ESI): m/z calcd for C9H12O3Na+ [M + Na]+: 191.0679; found: 191.0689.


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1-(5-(Hydroxymethyl)furan-2-yl)-2-methylbut-3-en-1-ol (11)

Colorless oil; yield: 75%; following procedure 1.

FTIR (neat): 3338, 2930, 1658, 1386, 1241, 1184, 1099, 1006, 912, 793 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.15–6.10 (m, 2 H), 5.83–5.66 (m, 1 H), 5.16–4.97 (m, 2 H), 4.47–4.43 (m, 2.8 H), 4.34 (d, J = 8.0 Hz, 0.2 H), 3.17 (br s, 2 H), 2.67–2.62 (m, 1 H), 1.05 (d, J = 8.0 Hz, 2.4 H), 0.90 (d, J = 8.0 Hz, 0.6 H).

13C NMR (100 MHz, CDCl3): δ (major) = 155.4, 153.3, 139.8, 115.6, 108.2, 107.6, 71.4, 57.2, 42.8, 15.3; δ (minor) = 155.0, 153.6, 140.1, 116.7, 108.0, 107.6, 71.4, 57.2, 43.3, 16.4.

HRMS (ESI): m/z calcd for C10H14O3Na+ [M + Na]+: 205.0836; found: 205.0844.


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1-(5-(Hydroxymethyl)furan-2-yl)-2,2-dimethylbut-3-en-1-ol (12)

Colorless oil; yield: 79%; following procedure 1.

FTIR (neat): 3342, 2964, 1637, 1462, 1413, 1361, 1184, 1000, 911 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.23 (d, J = 3.0 Hz, 1 H), 6.17 (d, J = 5.4 Hz, 1 H), 5.92 (dd, J = 17.5, 10.8 Hz, 1 H), 5.15–5.08 (m, 2 H), 4.55 (s, 2 H), 4.39 (s, 1 H), 2.16 (br s, 1 H), 1.98 (br s, 1 H), 1.07 (s, 3 H), 1.03 (s, 3 H).

13C NMR (100 MHz, CDCl3): δ = 154.7, 153.1, 144.4, 113.8, 108.3, 108.2, 75.1, 57.3, 42.1, 23.8, 22.4.

HRMS (ESI): m/z calcd for C11H16O3Na+ [M + Na]+: 219.0992; found: 219.0998.


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1-(5-(Hydroxymethyl)furan-2-yl)-3-methylbut-3-en-1-ol (13)

Colorless oil; yield: 80%; following procedure 1.

FTIR (neat): 3339, 2916, 1648, 1558, 1440, 1375, 1191, 1008, 891, 792 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.18 (d, J = 2.9 Hz, 1 H), 6.16 (d, J = 3.0 Hz, 1 H), 4.87 (s, 1 H), 4.80 (s, 1 H), 4.79–4.75 (m, 1 H), 4.50 (s, 2 H), 2.94 (s, 2 H), 2.53 (d, J = 7.1 Hz, 2 H), 1.73 (s, 3 H).

13C NMR (100 MHz, CDCl3): δ = 156.1, 153.4, 141.6, 114.0, 108.4, 106.8, 65.4, 57.2, 43.8, 22.3.

HRMS (ESI): m/z calcd for C10H14O3Na+ [M + Na]+: 205.0836; found: 205.0848.


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1-(5-(Hydroxymethyl)furan-2-yl)-3-methylenepentan-1-ol (14)

Colorless oil; yield: 76%; following procedure 1.

FTIR (neat): 3311, 2963, 2933, 1645, 1434, 1239, 1189, 1005, 891, 789 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.23–6.20 (m, 2 H), 4.92 (s, 1 H), 4.88 (s, 1 H), 4.80 (dd, J = 4.0, 8.0 Hz, 1 H), 4.58 (s, 2 H), 2.59 (t, J = 8.0 Hz, 2 H), 2.05–2.04 (m, 2 H), 1.05 (t, J = 8.0 Hz, 3 H).

13C NMR (100 MHz, CDCl3): δ = 156.1, 153.5, 147.2, 111.5, 108.3, 106.8, 65.6, 57.1, 42.4, 28.6, 12.2.

HRMS (ESI): m/z calcd for C11H16O3Na+ [M + Na]+: 219.0992; found: 219.1014.


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Methyl 4-Hydroxy-4-(5-(hydroxymethyl)furan-2-yl)-2-methylenebutanoate (15)

Colorless oil; yield: 90%; following procedure 1.

FTIR (neat): 3481, 2954, 1708, 1630, 1438, 1309, 1202, 1141, 947, 733 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.15 (s, 1 H), 6.08 (dd, J = 7.6, 3.0 Hz, 2 H), 5.57 (s, 1 H), 4.82–4.61 (m, 1 H), 4.41 (s, 2 H), 3.92 (s, 1 H), 3.81 (s, 1 H), 3.66 (s, 3 H), 2.79–2.67 (m, 2 H).

13C NMR (100 MHz, CDCl3): δ = 167.9, 155.6, 153.6, 136.1, 128.6, 108.1, 106.9, 66.3, 56.9, 52.1, 38.2.

HRMS (ESI): m/z calcd for C11H14O5Na+ [M + Na]+: 249.0733; found: 249.0754.


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Cyclohex-2-en-1-yl(5-(hydroxymethyl)furan-2-yl)methanol (16)

Colorless oil; yield: 75%; following procedure 1.

FTIR (neat): 3436, 2921, 2851, 1567, 1448, 1220, 1063, 1019, 879, 781 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.22–6.17 (m, 2 H), 5.89–5.86 (m, 0.25 H), 5.81–5.78 (m, 1 H), 5.38 (d, J = 12.0 Hz, 0.75 H), 4.56 (s, 2 H), 4.48 (d, J = 8.0 Hz, 0.75 H), 4.44 (d, J = 8.0 Hz, 0.25 H), 2.64 (br s, 1 H), 2.20 (br s, 2 H), 1.99 (s, 2 H), 1.86–1.74 (m, 2 H), 1.59–1.48 (m, 2 H).

13C NMR (100 MHz, CDCl3): δ (major) = 155.8, 153.5, 130.3, 127.3, 108.5, 107.8, 71.4, 57.6, 40.7, 25.3, 24.6, 21.1; δ (minor) = 156.1, 153.5, 130.6, 126.6, 108.5, 107.4, 71.9, 57.6, 40.5, 26.0, 25.2, 21.5.

HRMS (ESI): m/z calcd for C12H16O3Na+ [M + Na]+: 231.0992; found: 231.1004.


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1-(5-(Hydroxymethyl)furan-2-yl)but-3-yn-1-ol (17)

Colorless oil; yield: 63%; following procedure 1.

FTIR (neat): 3285, 2918, 1700, 1557, 1418, 1363, 1191, 1005, 855, 795 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.29 (d, J = 4.0 Hz, 1 H), 6.25 (d, J = 4.0 Hz, 1 H), 4.85 (d, J = 4.0 Hz, 1 H), 4.58 (s, 2 H), 2.78–2.76 (m, 2 H), 2.59 (br s, 1 H), 2.08–2.01 (m, 2 H).

13C NMR (100 MHz, CDCl3): δ = 154.8, 153.8, 108.6, 107.6, 80.3, 71.2, 66.1, 57.2, 25.9.

HRMS (ESI): m/z calcd for C9H10O3Na+ [M + Na]+: 189.0523; found: 189.0531.


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Synthesis of Allyl-Substituted DFF Derivatives (Using Zn); General Procedure 2

DFF (124.1 mg, 1.0 mmol) was dissolved in THF (2.0 mL). Saturated NH4Cl solution (1.0 mL) was added. Activated Zn (261.6 mmol, 4.0 mmol) was added to this reaction mixture and the heterogeneous mixture was stirred vigorously. Allyl bromide (3.0 mmol) was added dropwise. After completion of the reaction (monitored by TLC), the reaction mixture was diluted with ethyl acetate (6.0 mL) and sodium sulfate was added. The ethyl acetate layer was filtered through Celite and the filtrate was concentrated by rotary evaporator to obtain the crude product. The crude material was purified by silica gel flash chromatography (ethyl acetate–hexane, 1:2 to 2:3) and the pure product was obtained generally as a colorless oil.


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1,1¢-(Furan-2,5-diyl)bis(but-3-en-1-ol) (19)

Light yellow oil; yield: 82%; following procedure 2.

FTIR (neat): 3332, 2913, 1707, 1641, 1431, 1312, 1188, 1009, 911, 791 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.19 (s, 2 H), 5.84–5.77 (m, 2 H), 5.20–5.13 (m, 4 H), 4.73 (t, J = 8.0 Hz, 2 H), 2.62–2.60 (m, 4 H), 2.10 (br s, 2 H).

13C NMR (100 MHz, CDCl3): δ = 155.4, 155.3, 133.9, 118.0, 106.7, 106.6, 66.9, 39.8.

HRMS (ESI): m/z calcd for C12H16O3Na+ [M + Na]+: 231.0992; found: 231.0998.


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1,1¢-(Furan-2,5-diyl)bis(2-methylbut-3-en-1-ol) (20)

Light yellow oil; yield: 77%; following procedure 2.

FTIR (neat): 3363, 2968, 1666, 1640, 1455, 1416, 1373, 1235, 1187, 1110, 1008, 912 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.12–6.06 (m, 2 H), 5.79–5.62 (m, 2 H), 5.13–4.95 (m, 4 H), 4.43–4.29 (m, 2 H), 3.02 (br s, 1 H), 2.92 (br s, 1 H), 2.63 (q, J = 8.0 Hz, 2 H), 1.01 (t, J = 8.0 Hz, 5 H), 0.88 (t, J = 8.0 Hz, 1 H).

13C NMR (100 MHz, CDCl3): δ (major) = 154.6, 154.4, 139.8, 139.7, 115.5, 115.4, 107.4, 107.2, 71.4, 71.3, 42.9, 42.8, 15.4, 15.1.

HRMS (ESI): m/z calcd for C14H20O3Na+ [M + Na]+: 259.1305; found: 259.1315.


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1,1¢-(Furan-2,5-diyl)bis(2,2-dimethylbut-3-en-1-ol) (21)

Colorless oil; yield: 76%; following procedure 2.

FTIR (neat): 3443, 2966, 1637, 1502, 1469, 1414, 1363, 1148, 1006, 914, 730 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.18 (d, J = 4.0 Hz, 2 H), 5.92 (dt, J = 31.2, 12.7 Hz, 2 H), 5.14–5.07 (m, 4 H), 4.38 (s, 2 H), 2.05 (br s, 1 H), 2.00 (br s, 1 H), 1.07 (s, 6 H), 1.03 (s, 6 H).

13C NMR (100 MHz, CDCl3): δ = 153.9, 153.7, 144.3, 114.0, 113.9, 108.0, 75.0, 75.0, 42.1, 23.8, 23.7, 22.3, 22.2.

HRMS (ESI): m/z calcd for C16H24O3Na+ [M + Na]+: 287.1618; found: 287.1628.


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1,1¢-(Furan-2,5-diyl)bis(3-methylbut-3-en-1-ol) (22)

Colorless oil; yield: 82%; following procedure 2.

FTIR (neat): 3351, 2934, 1659, 1438, 1374, 1243, 1045, 1009, 891, 793 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.20 (s, 2 H), 4.91 (s, 2 H), 4.85–4.81 (m, 4 H), 2.57 (d, J = 10.9 Hz, 4 H), 2.10 (br s, 2 H), 1.76 (s, 6 H).

13C NMR (100 MHz, CDCl3): δ = 155.6, 155.5, 141.6, 113.9, 106.6, 106.5, 65.4, 43.9, 22.3.

HRMS (ESI): m/z calcd for C14H20O3Na+ [M + Na]+: 259.1305; found: 259.1312.


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Dimethyl 4,4¢-(Furan-2,5-diyl)bis(4-hydroxy-2-methylenebutanoate) (23)

Colorless oil; yield: 85%; following procedure 2.

FTIR (neat): 3429, 2954, 1709, 1630, 1438, 1200, 1139, 1012, 949, 730 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.15 (s, 1 H), 6.06 (s, 1 H), 5.58 (s, 1 H), 4.75 (dd, J = 12.8, 5.3 Hz, 1 H), 3.68 (s, 3 H), 3.48 (d, J = 4.0 Hz, 1 H), 2.83–2.58 (m, 2 H).

13C NMR (100 MHz, CDCl3): δ = 167.8, 155.2, 136.2, 128.5, 106.6, 77.5, 77.2, 76.8, 66.4, 52.1, 38.3.

HRMS (ESI): m/z calcd for C16H20O7Na+ [M + Na]+: 347.1102; found: 347.1125.


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Furan-2,5-diylbis(cyclohex-2-en-1-ylmethanol) (24)

Colorless oil; yield: 75%; following procedure 2.

FTIR (neat): 3357, 2914, 1647, 1442, 1375, 1046, 1010, 889 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.21–6.19 (m, 2 H), 5.88–5.74 (m, 2.4 H), 5.41–5.37 (m, 1.6 H), 4.52–4.44 (m, 2 H), 2.64 (br s, 2 H), 1.99 (br s, 6 H), 1.89–1.74 (m, 4 H), 1.63–1.50 (m, 4 H).

13C NMR (100 MHz, CDCl3): δ (major) = 155.0, 130.3, 127.3, 107.7, 71.4, 40.9, 25.3, 24.7, 21.1; δ (minor) = 155.4, 130.6, 126.5, 107.1, 71.9, 40.7, 25.9, 24.7, 21.5.

HRMS (ESI): m/z calcd for C18H24O3Na+ [M + Na]+: 311.1618; found: 311.1626.


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1,1¢-(Propane-2,2-diylbis(furan-5,2-diyl))bis(but-3-en-1-ol) (28)

Light yellow oil; yield: 82%; following procedure 2.

FTIR (neat): 3382, 2979, 1693, 1642, 1550, 1384, 1191, 1017, 908, 790, 728 cm–1.

1H NMR (400 MHz, CDCl3): δ = 6.14 (d, J = 3.1 Hz, 1 H), 5.93 (d, J = 3.1 Hz, 1 H), 5.82–5.75 (m, 1 H), 5.17–5.10 (m, 2 H), 4.69 (t, J = 6.5 Hz, 1 H), 2.61–2.57 (m, 2 H), 2.01 (br s, 1 H), 1.62 (s, 3 H).

13C NMR (100 MHz, CDCl3): δ = 159.4, 154.7, 133.9, 118.3, 106.5, 104.7, 67.0, 40.0, 37.5, 26.3.

HRMS (ESI): m/z calcd for C19H24O4Na+ [M + Na]+: 339.1567; found: 339.1567.


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1,1¢-(Cyclohexane-1,4-diyl)bis(but-3-en-1-ol) (41)

Colorless oil; yield: 85%; following procedure 2.

FTIR (neat): 3377, 2975, 1639, 1450, 1433, 1270, 1039, 984, 909, 863 cm–1.

1H NMR (400 MHz, CDCl3): δ = 5.83 (dt, J = 15.2, 8.1 Hz, 2 H), 5.14 (dd, J = 10.8, 5.5 Hz, 4 H), 3.75–3.09 (m, 2 H), 2.49–2.30 (m, 2 H), 2.18–2.04 (m, 2 H), 1.97 (s, 1 H), 1.80–1.72 (m, 1 H), 1.68–1.45 (m, 5 H), 1.32 (s, 2 H), 1.16–1.02 (m, 3 H).

13C NMR (100 MHz, CDCl3): δ = 135.4, 135.2, 118.5, 118.2, 74.7, 71.7, 43.1, 40.9, 39.5, 39.1, 28.8, 28.7, 27.8, 27.7, 25.7, 24.7.

HRMS (ESI): m/z calcd for C14H24O2Na+ [M + Na]+: 247.1669; found: 247.1674.


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1,1¢-(Cyclopentane-1,3-diyl)bis(but-3-en-1-ol) (43)

White solid; mp 85–87 °C; yield: 80%; following procedure 2.

FTIR (neat): 3335, 3262, 2902, 1643, 1494, 1246, 1133, 1044, 982, 870 cm–1.

1H NMR (400 MHz, CDCl3): δ = 5.84 (dt, J = 17.0, 7.5 Hz, 1 H), 5.15–5.06 (m, 2 H), 3.53–3.39 (m, 1 H), 2.37–2.32 (m, 1 H), 2.16–2.08 (m, 1 H), 2.06–1.97 (m, 1 H), 1.82 (s, 1 H), 1.75–1.65 (m, 1 H), 1.45–1.38 (m, 1 H), 1.30–1.20 (m, 1 H).

13C NMR (100 MHz, CDCl3): δ = 135.25, 118.1, 74.7, 45.6, 41.0, 31.7, 28.3.

HRMS (ESI): m/z calcd for C13H22O2Na+ [M + Na]+: 233.1512; found: 233.1529.


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Conflict of Interest

The authors declare no conflict of interest.

Acknowledgment

We thank Dr. Hari Subramanian for editorial assistance.

Supporting Information

    Supporting information for this article is available online at https://doi-org.accesdistant.sorbonne-universite.fr/10.1055/a-2241-6966.
  • Supporting Information

CorrespondingAuthor

Mukund P. Sibi
Department of Chemistry and Biochemistry, North Dakota State University
Fargo, North Dakota 58108
USA   

Publication History

Received: 17 November 2023

Accepted after revision: 10 January 2024

Accepted Manuscript online:
10 January 2024

Article published online:
14 February 2024

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Scheme 1 Synthesis of biomass-based diols
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Scheme 2 Zn-mediated allylation reaction with HMF (1)
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Scheme 3 Zn-mediated allylation reaction with DFF (18)
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Scheme 4 Grignard reaction with DFF (18)
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Scheme 5 Bi-mediated monoallylation reaction with DFF (18)
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Scheme 6 Selective allylation reactions with other aromatic dialdehydes
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Scheme 7 Unsymmetrical allylation from monoallyl-substituted DFF derivative 31
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Scheme 8 Hydrogenation of allylation derivatives
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Scheme 9 Chemoselective hydrogenation