Malic Acid as a Chiral Synthon: Synthesis of 1,2 and 1,3 Optically Active Diols

Thiam, M.; Slassi, Abdelmalik; Chastrette, F.; Amouroux, R.

doi:10.1080/00397919208021080

Cited by 41 publications

(9 citation statements)

References 18 publications

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“…9 Indeed, the BMS complex with NaBH 4 led to the reduction of an ester site with a b-oxygenated center. In this direction, we envisaged a possibility of access mono-reduction of ester functionality, controlling the amount of BMS added, as an expedient route to the preparation of synthon 3.…”

Section: Resultsmentioning

confidence: 99%

Efficient synthesis of 1,3,5-oxygenated synthons from dimethyl 3-oxoglutarate: first use of borane-dimethyl sulfide complex as a regioselective reducing agent of 3-oxygenated glutarate derivatives

Riatto¹,

Carneiro²,

Carvalho³

et al. 2011

J. Braz. Chem. Soc.

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A redução seletiva do 3-oxoglutarato de dimetila foi realizada em vários níveis. A redução quimiosseletiva da carbonila cetônica com boridreto de sódio é descrita em alto rendimento, fornecendo o 3-hidroxiglutarato de dimetila. Quando o complexo borana-dimetil sulfeto (BMS) foi empregado como agente redutor, um diol ou um triol puderam ser obtidos, respectivamente, a partir do 3-hidróxi-ou do 3-oxoglutarato, permitindo a síntese de compostos 1,3,5-oxigenados prática e eficientemente.The selective reduction of dimethyl 3-oxoglutarate was accomplished in different levels. A high yielding sodium borohydride reduction of the keto group is fully described leading to dimethyl 3-hydroxyglutarate. When borane-dimethyl sulfide (BMS) complex was used, a diol or a triol compound can be obtained by selective or total reduction of 3-hydroxy-or 3-oxoglutarate, respectively, allowing an efficient and practical route to 1,3,5-oxygenated compounds.

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Section: Resultsmentioning

confidence: 99%

Efficient synthesis of 1,3,5-oxygenated synthons from dimethyl 3-oxoglutarate: first use of borane-dimethyl sulfide complex as a regioselective reducing agent of 3-oxygenated glutarate derivatives

Riatto¹,

Carneiro²,

Carvalho³

et al. 2011

J. Braz. Chem. Soc.

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“…This was doubly done in this work: chemoselective and stereoselective reactions are now feasible since the two aldehydic moieties are differentiated and are part of a chiral molecule. It is worthy of note that other research groups initiated works on chiral form of glyoxal nearly at the same time: in each case one aldehyde function was masked as a hydrazone and the other one was transformed either in a dioxolane 15, 9 an acetal 16 10,11 or in an aminal 17. 12,13 This last work, due to Alexakis et al, was specially fruitful.…”

Section: Methodsmentioning

confidence: 99%

Asymmetric Synthesis of α-Amino Acids from a Chiral Masked Form of Glyoxal

Agami

Couty

Puchot-Kadouri

1998

Synlett

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Synthetic works devoted to the synthesis of α-amino acids are simply plethoric. The primary impetus which accounts for such a strong interest clearly is the potential of the target molecules to lead to practical applications associated with their biological interest. On the other hand, and this is a familiar rule in science, research towards this practical objective gave birth to the invention of new important synthetic methodologies and it can be stated that many achievements in this field are unquestionable landmarks in asymmetric synthesis. 1 Among the various methods that give access to optically active α-amino acids, one of the more documented consists in the use of electrophilic glycine equivalents. Fiaud and Kagan, as early as 1970, pioneered this field by reacting Grignard reagents with chiral imines. 2 Since then, this area expanded very rapidly and the syntheses using bis-lactim ethers and oxazinones developed respectively by Schöllkopf's and Williams' groups 3,4 are now considered as classical.In this respect, we have presented a chiral masked form of glyoxal derived from β-amino alcohols. This is another electrophilic glycine equivalent which appeared as an extremely convenient tool for the design of enantiopure acyclic as well as cyclic α-amino acids. This methodology is based on desymmetrization of glyoxal which was transformed into a chiral template. The crucial step of this procedure involves an iminium ion derived from one aldehyde function of glyoxal. This iminium ion was used as a substrate by applying either one of the following processes: (i) intermolecular addition of organozinc reagents or silyl derivatives, (ii) intramolecular ene-iminium reactions entailing an ene moiety linked to the template. Acyclic N-methyl amino acids resulted from the first process whereas the second one afforded proline or pipecolic acid-derived amino acids. In both cases, the reactions between the iminium moiety and its nucleophilic partner occurred with complete stereocontrol. The more significant aspects of this research are presented here. Condensation of glyoxal with chiral β-amino alcoholsWe have been interested for a long time in the stereoselective formation of oxazolidines 1 which result from the condensation of β-amino alcohols with aldehydes. 5 In the case of glyoxal however, it was reported by Le Rouzic et al. 6 , on the basis of X-ray analysis, that similar condensations afforded a 6-membered ring compound 2 (Scheme 1). Treated with thiophenol, heterocycle 2 was cleaved and yielded morpholine derivative 3. Scheme 1This fact strongly attracted our attention because compound 3 can be envisioned as a masked form of glyoxal in which the two original aldehydic functions are now discriminated. We thought that the use of chiral β-amino alcohols would afford a further interesting differentiation, i.e. between the enantiofaces of the glyoxal carbonyl groups.Abstract: Enantiopure acyclic and cyclic α-amino acids were synthesized from glyoxal. This dialdehyde was desymmetrized by condensing it with various (R)-ph...

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“…[44] The synthesis featured an exo-radical cyclization as ak ey stereocontrol element in the synthesis of the trans-b-lactone. The synthesis began with 1,3-benzylidene-protected diol 119,w hich was preparedf rom either S-malic acid 47 [45] or dodecanal 56,v ia aS harpless epoxidation. [46] Regioselective, reductive opening of 119 with DIBAL-Hg ave alcohol 121.S wern oxidation and acetylide anion addition of alcohol 121 gave a1 :1 mixture of diastereomers 122 a and 122 b,t he undesired isomer of which was converted into 122 b by Mitsunobu esterification.…”

Section: Yadav'ssynthesis2 006mentioning

confidence: 99%

The Asymmetric Synthesis of Tetrahydrolipstatin

2015

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The various syntheses of the over-the-counter anti-obesity drug tetrahydrolipstatin (also known as Orlistat) are reviewed. The 31 various syntheses cover the development of enantioselective natural products synthesis since the first synthesis of tetrahydrolipstatin (THL) by Schneider in 1987. After Schneider'sl andmark synthetic effort there have been numeroust otal and formal syntheses of THL, which have involvedadiverse range of approaches. These various syntheses can be classified by the methodst hat were used to install the stereochemistry,f or instance, chiral auxiliary,a symmetrica ldol, asymmetric allylation/crotylation, asymmetricr eductions,a symmetricr esolutions, asymmetric oxidations, and chiron approach. These routes also feature the elegant use of ac hiral phosphate template, at andem [2+ +2]-Mukaiyama aldol-lactonization, an anti-aldol segment via an on-aldol route, aP rins cyclization,a nd an epoxide carbonylation.

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Malic Acid as a Chiral Synthon: Synthesis of 1,2 and 1,3 Optically Active Diols

Cited by 41 publications

References 18 publications

Efficient synthesis of 1,3,5-oxygenated synthons from dimethyl 3-oxoglutarate: first use of borane-dimethyl sulfide complex as a regioselective reducing agent of 3-oxygenated glutarate derivatives

Efficient synthesis of 1,3,5-oxygenated synthons from dimethyl 3-oxoglutarate: first use of borane-dimethyl sulfide complex as a regioselective reducing agent of 3-oxygenated glutarate derivatives

Asymmetric Synthesis of α-Amino Acids from a Chiral Masked Form of Glyoxal

The Asymmetric Synthesis of Tetrahydrolipstatin

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