Cut and sew: benzofuran-ring-opening enabled cyclopentenone ring formation

Wang, Kai; Jiang, Chenghao; Zhang, Zhenming; Han, Chao; Wang, Xuewei; Li, Yaping; Chen, Kaiting; Zhao, Junfeng

doi:10.1039/d0cc05271j

Cited by 16 publications

(8 citation statements)

References 30 publications

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“…Natural or synthetic carbo-and heterocycles represent one of the most abundant compounds with biological activities for various therapeutic uses, [1,2] application in materials science, [3] and as substrates for a new transformation. [4][5][6] In particular, five-and six-membered N-, O-heterocycles have been received greater attention because of the diversity of applications related to their structures. [7][8][9][10] Several synthetic protocols have been reported to date for the construction of carbo-and heterocycles, which are based on inter-or intramolecular cyclization of open chain precursors.…”

Section: Introductionmentioning

confidence: 99%

“…Natural or synthetic carbo‐ and heterocycles represent one of the most abundant compounds with biological activities for various therapeutic uses, [1,2] application in materials science, [3] and as substrates for a new transformation [4–6] . In particular, five‐ and six‐membered N‐, O‐heterocycles have been received greater attention because of the diversity of applications related to their structures [7–10] .…”

Section: Introductionmentioning

confidence: 99%

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Selective 5‐Exo‐Dig versus 6‐Endo‐Dig Cyclization of Benzoimidazole Thiols with Propargyl Alcohols

et al. 2022

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We describe here the Lewis acid‐promoted cyclization reaction of benzomidazole thiols with propargyl alcohols for the selective synthesis of benzoimidazolo thiazines and benzothiazolo imidazoles. The reaction is regioselective and the solvent controls the formation of products. The systematic study to determine the best reaction conditions revealed that the six‐membered benzoimidazolo thiazines were obtained by reacting the benzoimidazole thiols with propargyl alcohols in the presence of boron trifluoride etherate, using dichloromethane as the solvent. Replacement of dichloromethane with dimethylformamide, by using the same starting material and reagents, gave selectively the five‐membered benzothiazolo imidazoles. The mechanism of this cyclization was proposed based on the results obtained and several control experiments.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Selective 5‐Exo‐Dig versus 6‐Endo‐Dig Cyclization of Benzoimidazole Thiols with Propargyl Alcohols

et al. 2022

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“…Cyclopentenones are widely considered a key backbone in biologically active natural products. Over the past decades, efficient synthetic strategies have been explored in the organic chemistry field. , Among them, 2-cyclopenten-1-one (2CP), which is a C 5 H 6 O ketone with a single double bond in the aliphatic pentagonal ring, has been an important precursor in organic syntheses because of its versatile functionality. 2CP can be found in many natural products, such as jasmone and punaglandins. , Owing to its high solubility in water, 2CP has recently become a subject of pharmaceutical research because of its potential as an ideal material to overcome drug transfer and pharmacological problems. , As a result, related studies have been expanded to measure cytotoxic activities in cancer .…”

Section: Introductionmentioning

confidence: 99%

Probing the Photoionization Dynamics of 2-Cyclopenten-1-one via High-Resolution VUV-MATI Spectroscopy

2021

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2-Cyclopenten-1-one (2CP), which is a cyclic enone, has been considered an important precursor because of its versatile functionality in the synthesis of natural products and materials for biofuels. Here, we report the adiabatic ionization energy (AIE) and cationic structure of 2CP in the ionic transition between the neutral S 0 and the cationic D 0 states probed by highresolution vacuum ultraviolet mass-analyzed threshold ionization (VUV-MATI) spectroscopy. From the 0−0 band position in the VUV-MATI spectrum supported by the VUV-photoionization efficiency curve, the AIE of 2CP was determined to be 9.3477 ± 0.0004 eV (75,395 ± 3 cm −1 ), which is in good agreement with the reference value but much more accurate. The measured MATI spectrum combined with the Franck−Condon fitting at the B3LYP/cc-pVTZ level revealed that the cationic structure of 2CP is twisted with the C 1 symmetry, whereas the neutral 2CP has the C S symmetry. The results indicate that geometrical changes induced by ionization are mainly attributed to the electron removal from the highest occupied molecular orbital, which consists of nonbonding orbitals on the oxygen atom in the carbonyl group interacting with the σ orbitals in the molecular plane of 2CP. Consequently, lowering the C 1 symmetry for cationic 2CP led to the promotions of the ring-bending and ring-twisting modes in the MATI spectrum, which correspond to the ring puckering and CC twisting in the S 0 state, respectively.

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“…As fundamental structural scaffolds, cyclopentenones [18][19][20][21][22][23] and dihydropyranones [24][25][26][27][28][29] widely exist in numerous natural products, biologically active compounds, and drugs, such as the antibiotics pentenomycins 18 and antitumor active (+)-altholactone 24 (Fig. 1c).…”

Section: Introductionmentioning

confidence: 99%

Solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes: access to cyclopentenones and dihydropyranols

Zhu

Zheng

Zhang

et al. 2021

Preprint

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Divergent synthesis is a powerful strategy for the fast assembly of different molecular scaffolds from the identical starting materials. We describe here a novel solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes with sulfonyl chlorides for the direct construction of highly functionalized cyclopentenones and dihydropyranols that widely exist in bioactive molecules and natural products. Density functional theory calculations suggest that an unprecedented N,N-dimethylacetamide-assisted 1,2-hydrogen transfer of alkoxy radicals is responsible for the cyclopentenone formation, whereas a C-C cleavage accounts for the selective production of dihydropyranols in acetonitrile. Given the simple and mild reaction conditions, excellent functional group compatibility, forming up to four chemical bonds, and tunable selectivity, it may find wide applications in synthetic chemistry.

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Cut and sew: benzofuran-ring-opening enabled cyclopentenone ring formation

Abstract: A facile approach to the fully substituted cyclopentenones involving an unprecedented benzofuran-ring-opening is described. The cleavage of benzofuran endocyclic C2-O bond proceeded smoothly in the absence of any transition metal...

Cited by 16 publications

References 30 publications

Selective 5‐Exo‐Dig versus 6‐Endo‐Dig Cyclization of Benzoimidazole Thiols with Propargyl Alcohols

Selective 5‐Exo‐Dig versus 6‐Endo‐Dig Cyclization of Benzoimidazole Thiols with Propargyl Alcohols

Probing the Photoionization Dynamics of 2-Cyclopenten-1-one via High-Resolution VUV-MATI Spectroscopy

Solvent-controlled photocatalytic divergent cyclization of alkynyl aldehydes: access to cyclopentenones and dihydropyranols

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