Stereoselective Synthesis and Some Properties of New Chlorodiorganotin-Substituted Macrodiolides

Gerbino, Darío C.; Scoccia, Jimena; Koll, Liliana C.; Mandolesi, Sandra D.; Podestá, Julio C.

doi:10.1021/om200987t

Cited by 10 publications

(10 citation statements)

References 18 publications

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“…Their higher Lewis acidity (in comparison with the most commonly used hydrostannylation reagent Bu 3 SnH or Ph 3 SnH) leads to much better regio-and stereoselectivities. 17 Considering the formation of an intermediate with intramolecular coordination during the mechanistic steps of the radical halohydrostannation, this could result in a higher stereoselectivity or differences in the course of the reaction.…”

Section: Resultsmentioning

confidence: 99%

“…Taking into account that the stereoselectivity in radical reactions may be improved by temperature lowering [17,38], we studied the chlorohydrostannations of 1b at -78ºC using Et 3 B as a radical initiator (Method B, Table 3) but without success. We observed longer reaction times, lower yields and no improvement in the diastereomeric relation.…”

Section: Table 2 Radical Chlorohydrostannation Of 1a and 1b By Thermmentioning

confidence: 99%

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Synthesis, Characterization and Antifungal Assessment of Optically Active Bis-organotin Compounds Derived from (S)-BINOL Diesters

Costantino¹,

Neudörfl²,

Ocampo³

et al. 2019

CHEM

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Background: Organotin(IV) derivatives have appeared recently as potential biologically active metallopharmaceuticals exhibiting a variety of therapeutic activities. Hence, it is important to study the synthesis of new organotin compounds with low toxicity that may be of pharmacological interest. Objectives: This study focuses on the synthesis of new bis-stannylated derivatives with C2 symmetry that could be tested as antifungal agents against two clinical important fungal species, Cryptococcus neoformans and Candida albicans. Methods: The radical addition of triorganotin hydrides (R3SnH) and diorganotin chlorohydrides (R2ClSnH) to bis-α,β-unsaturated diesters derived from (S)-BINOL led to the corresponding new bis-stannylated derivatives with C2 symmetry. Nine pure organotin compounds were synthesized with defined stereochemistry. Four of them were enantiomerically pure and four were diastereoisomeric mixtures. Results: All new organotin compounds were fully characterized, those with phenyl ligands bonded to tin were the most active compounds against both the strains (Cryptococcus neoformans and Candida albicans), with activity parameters of IC50 close to those of the reference drug (amphotericin B). Conclusion: Nine pure organotin compounds with C2 symmetry were synthesized with defined stereochemistry and their antifungal properties were tested against two clinical important fungi with IC values close to those of the reference drug. The structure-containing preferably two or three phenyl groups joined to the tin atom were highly active against both the strains compared with those possessing tri-n-butyl groups.

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Section: Resultsmentioning

confidence: 99%

Section: Table 2 Radical Chlorohydrostannation Of 1a and 1b By Thermmentioning

confidence: 99%

Synthesis, Characterization and Antifungal Assessment of Optically Active Bis-organotin Compounds Derived from (S)-BINOL Diesters

Costantino¹,

Neudörfl²,

Ocampo³

et al. 2019

CHEM

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“…Then, we development the cyclohydrostannation reactions with diorganotin halohydride. 5 The use of diorganotin chlorohydrides leads to much more stereoselective cyclohydrostannations than those carried out using triorganotin hydrides. However, they are reactive extremely unstable and requires an extra step of synthesis.…”

Section: Methodsmentioning

confidence: 99%

“…Though many of the antibiotic macrolides have highly substituted complex structures, also the simple ones have properties that make them worth studying. 2 Macrocyclic structures with more than one ester linkage are also classified as macrolides. 3 A number of synthetic strategies and methodologies have been developed for macrolide synthesis.…”

Section: Introductionmentioning

confidence: 99%

A New Method for the Stereoselective Synthesis of Macrodiolides From TADDOL Derivatives

Costantino

Mandolesi

Koll

2014

Proceedings of the 18th International Electronic Conference on Synthetic Organic Chemistry

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In previous studies, we reported the stereoselective radical addition of organotin hydrides to unsaturated TADDOL diesters. These reactions occurred with intramolecular cyclization under inert atmosphere, radical initiator, toluene and 75°C with high yields and stereoselectivity depending on the reactivity and steric bulk of the organotin hydride employed. 1 Here, we decided to study a new method for the synthesis of these macrocycles through the radical addition of different triorganotin hydrides, R 3 SnH (R= Me, n-Bu, Ph; Neophyl), to the same unsaturated TADDOL diesters, in THF as solvent and under MW conditions. We compared these results with the previous reported method. 1 Under MW conditions, reactions were completed in very short time and neither the double hydrostannation nor the cyclopolymerization products were obtained in both cases. Furthermore, we evaluated the stereoselectivity by 119 Sn-NMR spectroscopic analysis in both methods.

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“…We have already reported a new method that enables the synthesis of 11-membered macrodiolides starting from TADDOL unsaturated diesters via a tandem cyclohydrostannation reaction using triorganotin hydrides and diorganotin chlorohydrides. The new macrocycles were obtained in high global yields and with very good diastereoselectivity [1,2]. We also studied the effect of changing the number and the steric volume of the substituents on the structure of the reaction products, i.e., macrocycles and/or diaddition products [3].…”

Section: Introductionmentioning

confidence: 99%

Stereoselective Hydrostannation of Diacrylate and Dimethacrylate Esters of Galactaric Acid Derivatives: Cyclohydrostannation vs. Diaddition

Terraza

Gerbino

Podestá

2018

22nd International Electronic Conference on Synthetic Organic Chemistry

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This paper reports a study on the free radical hydrostannation of ((4S,4′R,5R,5′S)-2,2,2′,2′-tetramethyl-[4,4′-bi(1,3-dioxolane)]-5,5′-diyl)bis(diphenyl methylene) diacrylate (1) and dimethacrylate (2) with triorganotin hydrides, R3SnH (R = Me, n-Bu, Ph). Preliminary investigations show that these reactions could lead to mixtures of products of cyclohydrostannation and/or mono- or diaddition according to the organotin hydrides employed and the reaction conditions used. The addition of Me3SnH to 1 afforded a mixture of three organotin compounds from which the pure new 13-membered macrodiolide 3 (48%) was obtained. The other two organotins could not be separated. The addition of n-Bu3SnH to diester 1 led to a mixture of two organotins, the one in major proportion (91%) being the product of diaddition 7. The minor product 6a (9%) could not be isolated pure. The hydrostannation of 1 with Ph3SnH led to one organotin: The product of diaddition 8. The hydrostannation of the dimethacrylate 2 with the organotin hydrides R3SnH (R = Me, n-Bu, Ph) under the same reaction conditions, led in the three cases to mixtures containing mainly diaddition products, and no cyclization products were detected. Some physical characteristics of the new compounds including selected values of 1H, 13C, and 119Sn NMRs are included.

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Stereoselective Synthesis and Some Properties of New Chlorodiorganotin-Substituted Macrodiolides

Cited by 10 publications

References 18 publications

Synthesis, Characterization and Antifungal Assessment of Optically Active Bis-organotin Compounds Derived from (S)-BINOL Diesters

Synthesis, Characterization and Antifungal Assessment of Optically Active Bis-organotin Compounds Derived from (S)-BINOL Diesters

A New Method for the Stereoselective Synthesis of Macrodiolides From TADDOL Derivatives

Stereoselective Hydrostannation of Diacrylate and Dimethacrylate Esters of Galactaric Acid Derivatives: Cyclohydrostannation vs. Diaddition

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