Ethyl acetate as an acetyl surrogate for the iodine catalyzed acetylation of alcohols

Basumatary, Grace; Bez, Ghanashyam

doi:10.1016/j.tetlet.2017.10.005

Cited by 10 publications

(7 citation statements)

References 28 publications

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“…Purification by column chromatography (hexanes/EtOAc, 10:1 v/v) afforded product 3j ; 93% (184 mg, 0,93 mmol) colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 5.82 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 5.09–4.82 (m, 2H), 4.07 (t, J = 6.8 Hz, 2H), 2.11–1.97 (m, 5H), 1.67–1.58 (m, 2H), 1.43–1.27 (m, 10H); 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ 171.1, 139.1, 114.1, 64.6, 33.7, 29.3, 29.1, 29.0, 28.8, 28.5, 25.8, 20.9. The 1 H and 13 C{ 1 H} NMR data were in accordance with those reported in the literature …”

Section: Methodssupporting

confidence: 89%

“…The 1 H and 13 C{ 1 H} NMR data were in accordance with those reported in the literature. 63 Cinnamyl Acetate (3k). Purification by column chromatography (hexanes/EtOAc, 10:1 v/v) afforded product 3k; 88% (143 mg, 0.88 mmol) colorless oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.44−7.24 (m, 5H), 6.68 (d, J = 15.9 Hz, 1H), 6.31 (dt, J = 15.8, 6.4 Hz, 1H), 4.76 (dd, J = 6.4, 1.2 Hz, 2H), 2.13 (s, 3H); 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ 170.7, 136.2, 134.2, 128.6, 128.0, 126.6, 123.2, 65.0, 20.9.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Evaluation of gem-Diacetates as Alternative Reagents for Enzymatic Regio- and Stereoselective Acylation of Alcohols

et al. 2021

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Geminal diacetates have been used as sustainable acyl donors for enzymatic acylation of chiral and nonchiral alcohols. Especially, it was revealed that geminal diacetates showed higher reactivity than vinyl acetate for hydrolases that are sensitive to acetaldehyde. Under optimized conditions for enzymatic acylation, several synthetically relevant saturated and unsaturated acetates of various primary alcohols were obtained in very high yields up to 98% without E/Z isomerization of the double bond. Subsequently, the acyl donor was recreated from the resulting aldehyde and reused constantly in acylation. Therefore, the developed process is characterized by high atomic efficiency. Moreover, it was shown that acylation using geminal diacetates resulted in remarkable regioselectivity by discriminating among the primary and secondary hydroxyl groups in 1-phenyl-1,3-propanediol providing exclusively 3-acetoxy-1-phenyl-propan-1-ol in good yield. Further, enzymatic kinetic resolution (EKR) and chemoenzymatic dynamic kinetic resolution (DKR) protocols were developed using geminal diacetate as an acylating agent, resulting in chiral acetates in high yields up to 94% with enantiomeric excesses exceeding 99%.

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Section: Methodssupporting

confidence: 89%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Evaluation of gem-Diacetates as Alternative Reagents for Enzymatic Regio- and Stereoselective Acylation of Alcohols

et al. 2021

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“…A moderate amount of ethoxybenzene was observed when using ethyl acetate, suggesting the presence of ethanol in the reaction, which was likely formed through the HI-catalyzed retro-condensation of ethyl acetate. 43 Considering the compatibility of DA with different solvents, we examined the use of H 2 O as a solvent. However, due to the exceptionally low solubility of I 2 in H 2 O compared with other solvents, the H 2 O-generated phenol yield was excluded from the linear plot (Figure 2).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Acetone underwent aldol condensation and yielded α,β-unsaturated ketones, catalyzed by the HI byproduct from DA and the dehydrating environment (see the mechanism in Figure S7). A moderate amount of ethoxybenzene was observed when using ethyl acetate, suggesting the presence of ethanol in the reaction, which was likely formed through the HI-catalyzed retro-condensation of ethyl acetate …”

Section: Resultsmentioning

confidence: 99%

Carbocation Mechanism Revelation of Molecular Iodine-Mediated Dehydrogenative Aromatization of Substituted Cyclic Ketones to Phenols

Jin,

Petrovic,

Huang

et al. 2024

J. Org. Chem.

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Dehydrogenative aromatization (DA) of cyclic ketones is central to the development of functionalized aromatic precursors and hydrogen transfer− related technologies. Traditional DA strategies require precious metals with oxidants and are typically performed at high temperatures (100−150 °C) to overcome the high energy barrier of aliphatic C−H bond activation. Recently, a mild alternative approach based on I 2 has been proposed to realize DA on substituted unsaturated cyclic ketones under ambient conditions. However, depending on the solvent, the product selectivity may vary between phenol ether and phenol, and the reaction mechanisms remain unclear. Herein, based on time-resolved proton nuclear magnetic resonance, DFT calculation, and mass spectrometric analyses, we established a unified mechanism to account for the product distribution. Through substrate scope and desorption electrospray ionization−mass spectrometry, we discovered the formation of a carbocation, which has been overlooked in previous studies. An expanded substrate scope study coupled with spectroscopic observation provided strong evidence to elucidate the formation mechanism and the location of the carbocation. With a renewed understanding of the mechanism, we achieved a phenolic product yield of 17−96% while controlling the selectivity. Moreover, some reactants could undergo DA in H 2 O, achieving 95−96% yield at below water-boiling temperature.

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“…Alternatively, transesterification using ethyl acetate (EtOAc) has attracted much attention in recent years, since the reaction can be environmentally friendly, ideally producing only ethanol as a byproduct. Therefore, many useful transesterification reactions of alcohols with ethyl acetate using LiAl(O n C 8 H 17 ) alumina, metallic sulfates, PPh 3 /CBr 4 , Ce(OTf) 4 , distannoxane, In/I 2 , K 5 CoW 12 O 40 ⋅3H 2 O, N ‐hetrocyclic carbene, silphos, H 3 PW 12 O 40 , Zn 4 (OCOCF 3 ) 6 O, amberlyst‐15, silica‐bonded N ‐propyl sulfamic acid, lanthanum(III) catalyst, NaO t Bu, KO t Bu, I 2 , and enzymes have been reported. However, since most of these reactions require heating or strong bases (Scheme (a)), the development of a reaction that proceeds under mild conditions (Scheme (b)) is desired.…”

Section: Introductionmentioning

confidence: 99%

Reformatsky Reagent Promoted Acetylation of Primary and Secondary Aliphatic Alcohols Using Ethyl Acetate as an Acetyl Donor

Fujihara

Nakata

2019

ChemistrySelect

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The reaction system of a Reformatsky reagent as a promoter and EtOAc as a solvent and acetyl donor was found to achieve efficient acetylation of a variety of primary and secondary aliphatic alcohols under mild conditions. The reaction can be carried out by a simple one-pot operation and does not require heating. The reaction shows a high tolerance for various functional groups and chemoselectivity, such that the phenolic hydroxyl groups do not react. Furthermore, the reaction can be used for gram-scale acetylation.

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Ethyl acetate as an acetyl surrogate for the iodine catalyzed acetylation of alcohols

Cited by 10 publications

References 28 publications

Evaluation of gem-Diacetates as Alternative Reagents for Enzymatic Regio- and Stereoselective Acylation of Alcohols

Evaluation of gem-Diacetates as Alternative Reagents for Enzymatic Regio- and Stereoselective Acylation of Alcohols

Carbocation Mechanism Revelation of Molecular Iodine-Mediated Dehydrogenative Aromatization of Substituted Cyclic Ketones to Phenols

Reformatsky Reagent Promoted Acetylation of Primary and Secondary Aliphatic Alcohols Using Ethyl Acetate as an Acetyl Donor

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