Photochemical addition of cyclic ethers/acetals to olefins using  BuOO Bu: Synthesis of masked ketones/aldehydes and diols

Hayakawa, Mamiko; Shimizu, Rina; Omori, Hajime; Shirota, Hisashi; Uchida, Kou; Mashimo, Hiroshi; Han, Xu; Yamada, Ryuusei; Niino, Seiya; Wakame, Yoshiki; Liu, Chuanxiang; Aoyama, Tadashi; Ouchi, Akihiko

doi:10.1016/j.tet.2020.131557

Cited by 12 publications

(6 citation statements)

References 97 publications

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“…The photolyses were performed using a radical initiator, di-tert-butyl peroxide (DTBP), and >290 nm light at room temperature under a nitrogen atmosphere. 12 The yields of the syn-and anti-isomers for each product were determined using NMR spectroscopy with naphthalene as an internal standard. The syn-and anti-isomers were isolated using column chromatography.…”

Section: Resultsmentioning

confidence: 99%

“…General procedure for the photolysis 12 A THF (2) (10 mL) solution of olefin (1a-f) (0.2 mmol) and DTBP (0.1 mmol) was introduced into a quartz cylindrical cell (diameter: 3 cm) equipped with a three-way stopcock. The three-way stopcock was connected to the cell, a nitrogen source, and small vacuum pump.…”

Section: Methodsmentioning

confidence: 99%

“…), and fumaric acid (1i, 0.8/1.0 d.r.). 12 However, previous studies on the addition reaction of a THF radical to 1a, using an Ir photoredox catalyst 13 and radical initiator (PhCOCO2H) 14 have been reported to show no diastereoselectivity (1/1 d.r. ), which are inconsistent with our results.…”

Section: Introductionmentioning

confidence: 98%

“…), 3asyn/3a-anti, was found to be 1.6/1.0; the syn and anti isomers were assigned according to the literature. 12 In contrast, the d.r. was very small during the addition of 2 to maleic acid (1g, 0.9/1.0 d.r.…”

Section: Introductionmentioning

confidence: 98%

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Diastereoselective photochemical radical addition of a cyclic ether to olefins: addition of THF radicals to dialkyl maleates

Hayakawa¹,

Aoyama²,

Ouchi³

2021

Arkivoc

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The diastereoselectivity of the addition reaction of a THF radical to dialkyl maleates, the stereochemistry of the carbon atoms at both sides of the newly formed C-C bonds, has still not been established; both the presence and absence of diastereoselectivity have been reported in previous studies and its origin has not been discussed. We have obtained clear evidence for the presence of diastereoselectivity in the addition reaction, in which the diastereoselectivity increases with an increase in the bulkiness of the alkyl groups. DFT calculations on the maleates showed the presence of one or two stable conformations, which depend on the bulkiness of the alkyl groups.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 98%

See 2 more Smart Citations

Diastereoselective photochemical radical addition of a cyclic ether to olefins: addition of THF radicals to dialkyl maleates

Hayakawa¹,

Aoyama²,

Ouchi³

2021

Arkivoc

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“…The situation changes dramatically, however, with 1,4-butendioic acid derivatives. In fact, aryl, [53] benzyl [54,55] and α-oxy radicals [56][57][58] were sparsely used for the functionalization of maleic/fumaric acids, albeit no decarboxylation took place in the reaction course. This behavior is confirmed also in the present work (with donors 2 o-2 v), however, the introduction of an electron-withdrawing group (such as an acyl moiety) is able to induce a clean decarboxylation to give a γ-keto acid (Scheme 4).…”

Section: Chemsuschemmentioning

confidence: 99%

Photocatalyzed Functionalization of Alkenoic Acids in 3D‐Printed Reactors

et al. 2022

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The valorization of alkenoic acids possibly deriving from biomass (fumaric and citraconic acids) was carried out through conversion in important building blocks, such as γ‐keto acids and succinic acid derivatives. The functionalization was carried out by addition onto the C=C double bond of radicals generated under photocatalyzed conditions from suitable hydrogen donors (mainly aldehydes) and by adopting a decatungstate salt as the photocatalyst. Syntheses were performed under batch (in a glass vessel) and flow (by using 3D‐printed reactors) conditions. The design of the latter reactors allowed for an improved yield and productivity.

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Acetal Radicals: Synthetic Access and Applications

Samony,

Kim

2023

ChemCatChem

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Aldehydes and ketones are two of the most versatile functional groups in organic synthesis, and the development of new reagents and protocols to install them are always warranted. Recently, the reemergence of radical chemistry has provided new opportunities to introduce these important carbonyl motifs. As such, acetal radicals can be employed as synthetic radical equivalents for acyl radicals that can also circumvent known stability challenges. This review aims to summarize the advancements and known uses of acetal radicals, as well as explore acetal radical formation and synthetic applications.

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Photochemical addition of cyclic ethers/acetals to olefins using BuOO Bu: Synthesis of masked ketones/aldehydes and diols

Cited by 12 publications

References 97 publications

Diastereoselective photochemical radical addition of a cyclic ether to olefins: addition of THF radicals to dialkyl maleates

Diastereoselective photochemical radical addition of a cyclic ether to olefins: addition of THF radicals to dialkyl maleates

Photocatalyzed Functionalization of Alkenoic Acids in 3D‐Printed Reactors

Acetal Radicals: Synthetic Access and Applications

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