Conformational Equilibria and Solvolyses of Six-Membered Ring Sulfoxide Derivatives

Martin, J. C.; Uebel, J. J.

doi:10.1021/ja01068a036

Cited by 70 publications

(13 citation statements)

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“…A point of particular interest is the configuration of the methyl group, sulfoxide oxygen, and carboxyl group with respect to the ring. The oxygen atom occupies the axial position, in agreement with that found for many other sulfoxides (Shearer, 1959;Johnson & McCants, 1964;Martin & Uebel, 1964;Cairns, Eglington & Gibson, 1964). The S-O bond distance of 1.492A is also in good agreement with the value found for (7) -0.3150 (6) 0.4378 (3) 0(9) 0-3606 (7) 0-2307 (4) O (10) 0.6186 (7) 0.2108 (4) (12) those sulfoxides where sulfur is bonded to two carbons and one oxygen (Abrahams, 1956;Shearer, 1959).…”

Section: Description Of the Stracturesupporting

confidence: 82%

The structure of cycloalliin hydrochloride monohydrate

Palmer¹,

Lee²

1966

Acta Crystallogr

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Section: Description Of the Stracturesupporting

confidence: 82%

The structure of cycloalliin hydrochloride monohydrate

Palmer¹,

Lee²

1966

Acta Crystallogr

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“…To determine the relative configuration of substitutions, the aromatic solvent-induced NMR shift 15,16) was used as in the case of onionin A. It is known that the conformational preference of the sulfoxide thermodynamically is axial form [17][18][19] (lower α-side) in Fig. 2.…”

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confidence: 99%

Garlicnins B1, C1, and D, from the Fraction Regulating Macrophage Activation of Allium sativum

et al. 2012

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Several novel sulfides from acetone extracts of bulbs of garlic (Allium sativum L.), were identified and investigated. These were named garlicnins B 1 (1), C 1 (2), and D (3), and they were found to have the ability to control macrophage activation. Garlicnins B 1 (1) and C 1 (2) possess a new skeleton of cyclic sulfoxide and their structures of garlicnins B 1 (1) and C 1 (2) were characterized as 3,4-dimethyltetrahydrothiophene-Soxide derivatives carrying the substitutions of a propenyl and a sulfenic acid, and an allyldithiine and a 1-propene-sulfenic acid (a), respectively. The mechanism of the proposed production of these compounds is discussed. Garlicnin D (3), dithiine-type, was estimated to be derived by addition of (a) allyl thiosulfenic acid (b) derived from allicin. The identification of these novel sufoxides from onion and garlic accumulates a great deal of new chemistry to the Allium sulfide field, and future pharmacological investigations aid the development of natural, healthy foods and anti-cancer agents that could potentially prevent or combat disease.Key words Allium sativum; sulfoxide; garlicnin B 1 ; garlicnin C 1 ; garlicnin D; macrophage activation Garlic, Allium sativum L. (Liliaceae) is at the top of the National Cancer Institute's list of designer foods that prevent cancer. The various biological activities of garlic are generally classified into two cases, cardiovascular disease prevention and cancer prevention. For the former, activities include the inhibition of cholesterol synthesis, platelet aggregation, and arterial smooth muscle cell proliferation inhibition as well as having anti-inflammatory, anti-oxidant, and hydrogen sulfide-mediated vasodilatory effects. Effects on carcinogen metabolism (enhanced cellular glutathione synthesis induced cell cycle arrest and apoptosis) and prevention of Helicobacter pylori infection, gastric cancer, and colorectal cancer make up the latter category.1-3) The chemistry of garlic sulfides is summarized in a text book editted by Block. 3,4) In previous work, we isolated a novel, stable sulfide, 3,4-dimethyl-5-(1-propenyl)-tetrahydrothiophene-2-sulfoxide-S-oxide, from the acetone extract of Allium cepa L. which was found to inhibit macrophage activation. We named this onionin A. 5)Here, sulfur-containing substances from an acetone-soluble extract of A. sativum L. have been isolated and characterized to aid the development of natural, healthy foods that potentially prevent and combat disease, in particular tumors.Chinese garlic (1061 g) was roughly chopped and blended in a mixer along with acetone. Subsequently, the mixture was soaked in acetone for 3 d at room temperature. The filtrate was evaporated at 40°C in vacuo to obtain a residue (26.1 g), which was then subjected to polystyrene gel column chromatography (Diaion HP-20). It was first eluted with water, then with methanol (residue after evaporation: 5.90 g), and finally with acetone (the residue after evaporation: 0.32 g). Part of the methanolic eluate (3.0 g) was partitioned between ethyl ace...

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“…It is known that the conformational preference of a sulfoxide is the axial form [21][22][23] (lower α-side). In 1 H-NMR analysis in C 6 D 6 , the molecule of 1 forms a collision complex 19) opposite to the sulfoxide, indicating that C 6 D 6 is oriented towards the opposite side (upper β-side) of the sulfoxide and affects the NMR chemical shifts.…”

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Cyclic Sulfoxides-Garlicnins K1, K2, and H1-Extracted from Allium sativum

et al. 2015

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Newly identified cyclic sulfoxides-garlicnins K 1 (1), K 2 (2), and H 1 (3)-were isolated from the acetone extracts of the bulbs of garlic, Allium sativum. Garlicnin H 1 (3) demonstrated potential to suppress tumor cell proliferation by regulating macrophage activation. The structures of garlicnins K 1 and K 2 , 3,4-dimethyl-5-allyl-tetrahydrothiophen-2-one-S-oxides, and the structure of garlicnin H 1 , 3-carboxy-3-hydroxy-4-methyl-5-allylsulfoxide-tetrahydrothiophen-2-(ethane-1,2-diol)-S-oxide were characterized by spectroscopic analysis.

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Conformational Equilibria and Solvolyses of Six-Membered Ring Sulfoxide Derivatives

Cited by 70 publications

References 0 publications

The structure of cycloalliin hydrochloride monohydrate

The structure of cycloalliin hydrochloride monohydrate

Garlicnins B<sub>1</sub>, C<sub>1</sub>, and D, from the Fraction Regulating Macrophage Activation of <i>Allium sativum</i>

Cyclic Sulfoxides-Garlicnins K<sub>1</sub>, K<sub>2</sub>, and H<sub>1</sub>-Extracted from <i>Allium sativum</i>

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