Systematic synthetic study of four diastereomerically distinct limonene-1,2-diols and their corresponding cyclic carbonates

Morikawa, Hiroshi; Yamaguchi, Junichi; Sugimura, Shun-ichi; Minamoto, Masato; Gorou, Yuuta; Morinaga, Hisatoyo; Motokucho, Suguru

doi:10.3762/bjoc.15.13

Cited by 18 publications

(32 citation statements)

References 32 publications

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“…The structure of compound 29 was confirmed by its five-membered cyclic carbonate 30 synthesized from 29 by the reaction with triphosgene (Scheme 2) [48]. It is well known that this carbonation reaction maintains the stereochemical configuration of 29 [49,50].…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands

Lê

Szilasi

Volford

et al. 2019

IJMS

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A library of isopulegol-based bi-, tri- and tetrafunctional chiral ligands has been developed from commercially available (−)-isopulegol and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. Michael addition of primary amines towards α-methylene-γ-butyrolactone, followed by reduction, was accomplished to provide aminodiols in highly stereoselective transformations. Stereoselective epoxidation of (+)-neoisopulegol, derived from natural (−)-isopulegol, and subsequent oxirane ring opening with primary amines afforded aminodiols. The regioselective ring closure of N-substituted aminodiols with formaldehyde was also investigated. Hydroxylation of (+)-neoisopulegol resulted in diol, which was then transformed into aminotriols by aminolysis of its epoxides. Dihydroxylation of (+)-neoisopulegol or derivatives with OsO4/NMO gave neoisopulegol-based di-, tri- and tetraols in highly stereoselective reactions. The antimicrobial activity of aminodiol and aminotriol derivatives as well as di-, tri- and tetraols was also explored. In addition, structure–activity relationships were examined by assessing substituent effects on the aminodiol and aminotriol systems.

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Section: Resultsmentioning

confidence: 99%

Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands

Lê

Szilasi

Volford

et al. 2019

IJMS

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“…For (+)-(1 S ,2 S ,4 R )- 6 : [α] D 25 = +25.3 ( c 2.7, CHCl 3 ), lit. [ 41 ] [α] D 25 = +25.8 ( c 1.0, CHCl 3 ); for (−)-(1 R ,2 R ,4 R )- 7 : [α] D 25 = −4.8 ( c 1.0, CHCl 3 ), lit. [ 39 ] [α] D 25 = −5.0 ( c 1.0, CHCl 3 ).…”

Section: Methodsmentioning

confidence: 99%

“…[α] D 25 = −25.1 ( c 2.3, CHCl 3 ), lit. [ 41 ] [α] D 25 = +25.8 ( c 1.0, CHCl 3 ) for its enantiomer.…”

Section: Methodsmentioning

confidence: 99%

Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds

2021

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Limonene is one of the most abundant naturally occurring cyclic monoterpenes and has recently emerged as a sustainable alternative to petroleum-based solvents as well as a chemical platform for the production of value-added compounds. The biocatalytic epoxidation of both enantiomers of limonene was carried out in the presence of a peroxygenase-containing preparation from oat (Avena sativa) flour. Different reaction profiles were observed depending on the starting enantiomer of limonene, but in both cases the 1,2-monoepoxide was obtained as the main product with excellent diastereoselectivity. Trans-1,2-monoepoxide and cis-1,2-monoepoxide were isolated from the reaction of (R)-limonene and (S)-limonene, respectively, and the reactions were scaled-up to 0.17 M substrate concentration. The process is valuable for operational simplicity, lack of toxic metal catalysts, and cost-effectiveness of the enzymatic source. Pure stereoisomers of 1,2-monoepoxides of limonene constitute a useful starting material for biorenewable polymers, but can be also converted into other chiral derivatives by epoxide ring opening with nucleophiles. As a proof of concept, a tandem protocol for the preparation of enantiopure (1S,2S,4R)-1,2-diol from (R)-limonene and (1R,2R,4S)-1,2-diol from (S)-limonene was developed.

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“…Since neither the hydrogenolysis of N-benzyl analogues 7-10 nor the formation of an oxazolidine ring system by ring closure with formaldehyde had an effect on the absolute configuration of C-3, the relative configuration of the chiral centers of 11-15 is known to be the same as that of 7-10 [64,65,68]. The syn-selective dihydroxylation of compound 3 with OsO4 in the presence of a stoichiometric amount of the co-oxidant, NMO (4-methylmorpholine N-oxide) produced product 6 as a single diastereomer in a moderate yield [68,69] (Scheme 1).…”

Section: Synthesis Of Ispulegol-based 12-aminoalcoholsmentioning

confidence: 99%

“…The stereochemistry of 11 and 12-15 was proven in a similar manner by 1D and 2D NMR measurements. The syn-selective dihydroxylation of compound 3 with OsO4 in the presence of a stoichiometric amount of the co-oxidant, NMO (4-methylmorpholine N-oxide) produced product 6 as a single diastereomer in a moderate yield [68,69] (Scheme 1).…”

Section: Synthesis Of Ispulegol-based 12-aminoalcoholsmentioning

confidence: 99%

Synthesis and Application of 1,2-Aminoalcohols with Neoisopulegol-Based Octahydrobenzofuran Core

et al. 2019

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A library of 1,2-aminoalcohol derivatives with a neoisopulegol-based octahydrobenzofuran core was developed and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. The allylic chlorination of (+)-neoisopulegol, derived from natural (-)-isopulegol followed by cyclization, gave the key methyleneoctahydrobenzofuran intermediate. The stereoselective epoxidation of the key intermediate and subsequent oxirane ring opening with primary amines afforded the required 1,2-aminoalcohols. The ring closure of the secondary amine analogues with formaldehyde provided spiro-oxazolidine ring systems. The dihydroxylation of the methylenetetrahydrofuran moiety with OsO 4 /NMO (4-methylmorpholine N-oxide) resulted in the formation of a neoisopulegol-based diol in a highly stereoselective reaction. The antimicrobial activity of both the aminoalcohol derivatives and the diol was also explored. Molecules 2020, 25, 21 2 of 14 antimalarial [26-28], and antileishmanial [29] agents. The 1,2-aminoalcohol function is found in a broad range of β-adrenergic blockers that are used extensively in the management of cardiovascular disorders [30], including hypertension, angina pectoris and cardiac arrhythmias, and other disorders that are related to the sympathetic nervous system [31,32]. 1,2-aminoalcohols have also been demonstrated to be excellent chiral auxiliaries and chiral catalysts in asymmetric synthesis [33]. To achieve new, efficient, and commercially available chiral catalysts, natural chiral terpenes, such as α-pinene [34-38], β-pinene [34,39], (-)-3-carene [39,40], (-)-verbenone [41,42], (-)-fenchone [43,44], (+)-camphor [43,45,46], and (-)-menthone [47] have proven to be excellent sources for the synthesis of bifunctional chiral compounds and heterocycles.In the present work, we set out to create a compound library with a (+)-neoisopulegol-based octahydrobenzofuran core and 1,2-aminoalcohol moieties. The synthesis started from commercially available (-)-isopulegol and then utilizing the resulting 1,2-aminoalcohol derivatives as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde. Furthermore, the antimicrobial activities of the synthesized compounds were also tested on multiple bacterial and fungal strains. Results Synthesis of Key Intermediate 3Key intermediate (-)-3-methylenetetrahydrofuran 3 was prepared from commercially available (-)-isopulegol 1 by oxidizing its hydroxyl function, followed by the stereoselective reduction of the resulting carbonyl group, thus providing (+)-neoisopulegol 2 [48][49][50][51]. The allylic chlorination of (+)-neoisopulegol 2 was followed by the cyclization-produced (-)-methylenetetrahydrofuran 3 [52-55], which was transformed into (−)-methylenetetrahydrofuran 4 by allylic oxidation after applying the literature method [55,56] (Figure 1).

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Systematic synthetic study of four diastereomerically distinct limonene-1,2-diols and their corresponding cyclic carbonates

Cited by 18 publications

References 32 publications

Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands

Stereoselective Synthesis and Investigation of Isopulegol-Based Chiral Ligands

Stereospecific Epoxidation of Limonene Catalyzed by Peroxygenase from Oat Seeds

Synthesis and Application of 1,2-Aminoalcohols with Neoisopulegol-Based Octahydrobenzofuran Core

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