Further study on synthesis of the cyclobakuchiols

Kawashima, Hidehisa; Sakai, Masahiro; Kaneko, Yuki; Kobayashi, Yuichi

doi:10.1016/j.tet.2015.02.092

Cited by 14 publications

(8 citation statements)

References 26 publications

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“…Thus, we established a practical enantioselective procedure to prepare both enantiomers of 4-hydroxy-2-cyclohexenone ( R )- and ( S )- 1a in four steps, ca. 44% overall yield and 92% ee, and their O -silyl derivatives, ( R )- and ( S )- 1b, in five steps and 60% overall yield, which compared with other published methodologies [ 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. Both enantiomers of the product could be obtained from the same precursor only by selecting either the ( S , S )- or ( R , R )- 5 catalyst.…”

Section: Resultsmentioning

confidence: 65%

“…Optically active ϒ-substituted cycloalkenones are compounds of synthetic importance that are used as precursors in the synthesis of natural products and pharmaceutically active molecules [ 1 , 2 , 3 , 4 ]. In particular, both enantiomers of 4-hydroxy-2-cyclohexenone 1a and their O -protected derivatives, such as 1b , c , have been extensively used in organic synthesis ( Figure 1 ) [ 5 , 6 , 7 ]. These chiral cycloalkenones have been prepared by different methodologies that involve enzymatic transformations [ 8 ], kinetic resolutions [ 9 ], chiral auxiliaries [ 10 ], asymmetric catalysis [ 11 ], or chiral pool compounds [ 12 , 13 ].…”

Section: Introductionmentioning

confidence: 99%

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Enantiocontrolled Preparation of ϒ-Substituted Cyclohexenones: Synthesis and Kinase Activity Assays of Cyclopropyl-Fused Cyclohexane Nucleosides

Jurado

Domı́nguez-Pérez

Illa

et al. 2022

IJMS

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The enantioselective preparation of the two isomers of 4-hydroxy-2-cyclohexanone derivatives 1a,b was achieved, starting from a common cyclohexenone, through asymmetric transfer hydrogenation (ATH) reactions using bifunctional ruthenium catalysts. From these versatile intermediates, a stereoselective route to a cytosine analogue built on a bicyclo [4.1.0]heptane scaffold is described. Nucleoside kinase activity assays with this cyclopropyl-fused cyclohexane nucleoside, together with other related nucleosides (2a–e), were performed, showing that thymine- and guanine- containing compounds have affinity for herpes simplex virus Type 1 (HSV-1) thymidine kinase (TK) but not for human cytosolic TK-1, thus pointing to their selectivity for herpetic TKs but not cellular TKs.

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Section: Resultsmentioning

confidence: 65%

Section: Introductionmentioning

confidence: 99%

Enantiocontrolled Preparation of ϒ-Substituted Cyclohexenones: Synthesis and Kinase Activity Assays of Cyclopropyl-Fused Cyclohexane Nucleosides

Jurado

Domı́nguez-Pérez

Illa

et al. 2022

IJMS

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“…The Prilezhaev (Prileschajew) method that uses m ‐chloroperoxybenzoic acid ( m CPBA) as an oxidant under mild conditions is applied to the epoxidation of botryococcene 1 , because it has been frequently used in the synthetic procedures of unstable natural products such as terpenoids ,. First, 1 is reacted with an excess amount of the oxidant so that all the C−C double bonds of 1 react.…”

Section: Figurementioning

confidence: 99%

“…Similarly, epoxidation is a widely used method for activation of alkenes by electrophilic addition,, which could be applied in derivatizations of terpenoids . An enzymatic epoxidation of an algal oil squalene has also been known as a key step for biosynthesis of cyclic triterpenes, In addition, produced epoxides would be reactive starting substances for various chemical materials such as thermosetting resins ,.…”

Section: Figurementioning

confidence: 99%

Selective Synthesis of Botryococcene Pentaepoxide ‐ The Chemical Modifications of the Algal Biomass Oil

Kawashima

Kijima

2018

ChemistrySelect

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A biomass oil, botryococcene ((E)‐2,3,7,10,13,16,20,21‐octamethyl‐6,17‐dimethylene‐10‐vinyldocosa‐1,11,21‐triene), produced from microalga “Botryococcus braunii” was epoxidized by Prilezaev reaction using excess amount of m‐chloroperoxybenzoic acid under mild conditions for the purpose of applicative derivatizations of the oil. The oil underwent epoxidations at the C2,6,17,21‐positioned four vinylidenes and C11‐12 vinylene site‐selectively except the electronically inactive C10‐vinyl, giving the botryococcene pentaepoxide in high yield.

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“…The synthesis of key intermediate (+)-nopinone ( 2 ), prepared from (–)-β-pinene by using RuCl 3 and NaIO 4 , was previously reported (Scheme 1 ). 19 20 21 22 Diastereoselective aldol condensation of 2-pyridinecarboxaldehyde with (+)-nopinone ( 2 ) under alkaline conditions provided α,β-unsaturated ketone 3 in 76% yield. Subsequent reduction of 3 with NaBH 4 in the presence of CeCl 3 led to the formation of compound 4 in high yield and stereoselectivity.…”

mentioning

confidence: 99%

Stereoselective Synthesis and Applications of Pinane-Based Chiral 1,4-Amino Alcohol Derivatives

et al. 2022

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A new library of pinane-based 1,4-amino alcohols was synthesised and utilised as chiral ligands in enantioselective diethylzinc addition to benzaldehyde. Aldol condensation of (+)-nopinone, derived from (–)-β-pinene, with 2-pyridinecarboxaldehyde gave the key intermediate α,β-unsaturated ketone, which was transformed in diastereoselective reduction, followed by hydrogenation, resulting in 1,4-amino alcohols. On the other hand, epoxidation of the α,β-unsaturated ketone, followed by reduction and then hydrogenation of the pyridine ring, afforded a mixture of 4-amino-2,3-epoxy-1-ols. Stereoselective hydride reduction of the epoxy ketone and subsequent condensation of the resulting products with substituted benzyl bromides provided quaternary ammonium salts, which were subjected to hydride reduction and then hydrogenation, affording 4-amino-2,3-epoxy-1-ol derivatives containing an N-benzylpiperidine moiety. The inhibition of nucleophile-initiated opening of the oxirane ring was interpreted by a systematic series of comparative Hartree–Fock modelling study using the 6-31+G(d,p) basis set. The antiproliferative activities of 4-amino-2,3-epoxy-1-ol derivatives were examined, and structure–activity relationships were studied from the aspects of the stereochemistry of the oxirane ring, saturation, and substituent effects on the piperidine ring system.

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Further study on synthesis of the cyclobakuchiols

Cited by 14 publications

References 26 publications

Enantiocontrolled Preparation of ϒ-Substituted Cyclohexenones: Synthesis and Kinase Activity Assays of Cyclopropyl-Fused Cyclohexane Nucleosides

Enantiocontrolled Preparation of ϒ-Substituted Cyclohexenones: Synthesis and Kinase Activity Assays of Cyclopropyl-Fused Cyclohexane Nucleosides

Selective Synthesis of Botryococcene Pentaepoxide ‐ The Chemical Modifications of the Algal Biomass Oil

Stereoselective Synthesis and Applications of Pinane-Based Chiral 1,4-Amino Alcohol Derivatives

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