Amine assisted enzymatic esterification of 1,2-diol monotosylates

Boaz, Neil W.; Zimmerman, R. L.

doi:10.1016/s0957-4166(00)86160-1

Cited by 25 publications

(10 citation statements)

References 5 publications

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“…Next, we attempted use of cyclohexylamine (CHA) to improve e.e. and productivity via dynamic kinetic resolution [ 27 , 28 ]. While monitoring the reaction by HPLC at CHA concentration of 3%, we noticed that at about 25% conversion, the product acid was obtained in about 70% e.e., but the major enantiomer had R configuration as opposed to IPA addition which produced major enantiomer in S configuration ( Fig 3A ).…”

Section: Resultsmentioning

confidence: 99%

Characterization of an Indole-3-Acetamide Hydrolase from Alcaligenes faecalis subsp. parafaecalis and Its Application in Efficient Preparation of Both Enantiomers of Chiral Building Block 2,3-Dihydro-1,4-Benzodioxin-2-Carboxylic Acid

Mishra¹,

Kaur²,

Sharma³

et al. 2016

PLoS ONE

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Both the enantiomers of 2,3-dihydro-1,4-benzodioxin-2-carboxylic acid are valuable chiral synthons for enantiospecific synthesis of therapeutic agents such as (S)-doxazosin mesylate, WB 4101, MKC 242, 2,3-dihydro-2-hydroxymethyl-1,4-benzodioxin, and N-[2,4-oxo-1,3-thiazolidin-3-yl]-2,3-dihydro-1,4-benzodioxin-2-carboxamide. Pharmaceutical applications require these enantiomers in optically pure form. However, currently available methods suffer from one drawback or other, such as low efficiency, uncommon and not so easily accessible chiral resolving agent and less than optimal enantiomeric purity. Our interest in finding a biocatalyst for efficient production of enantiomerically pure 2,3-dihydro-1,4-benzodioxin-2-carboxylic acid lead us to discover an amidase activity from Alcaligenes faecalis subsp. parafaecalis, which was able to kinetically resolve 2,3-dihydro-1,4-benzodioxin-2-carboxyamide with E value of >200. Thus, at about 50% conversion, (R)-2,3-dihydro-1,4-benzodioxin-2-carboxylic acid was produced in >99% e.e. The remaining amide had (S)-configuration and 99% e.e. The amide and acid were easily separated by aqueous (alkaline)-organic two phase extraction method. The same amidase was able to catalyse, albeit at much lower rate the hydrolysis of (S)-amide to (S)-acid without loss of e.e. The amidase activity was identified as indole-3-acetamide hydrolase (IaaH). IaaH is known to catalyse conversion of indole-3-acetamide (IAM) to indole-3-acetic acid (IAA), which is phytohormone of auxin class and is widespread among plants and bacteria that inhabit plant rhizosphere. IaaH exhibited high activity for 2,3-dihydro-1,4-benzodioxin-2-carboxamide, which was about 65% compared to its natural substrate, indole-3-acetamide. The natural substrate for IaaH indole-3-acetamide shared, at least in part a similar bicyclic structure with 2,3-dihydro-1,4-benzodioxin-2-carboxamide, which may account for high activity of enzyme towards this un-natural substrate. To the best of our knowledge this is the first application of IaaH in production of industrially important molecules.

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Section: Resultsmentioning

confidence: 99%

Characterization of an Indole-3-Acetamide Hydrolase from Alcaligenes faecalis subsp. parafaecalis and Its Application in Efficient Preparation of Both Enantiomers of Chiral Building Block 2,3-Dihydro-1,4-Benzodioxin-2-Carboxylic Acid

Mishra¹,

Kaur²,

Sharma³

et al. 2016

PLoS ONE

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“…As a consequence of the immediate hydrolysis product being water soluble, the diol 1 was obtained in a very pure state and separation from organic impurities was easily achieved. Methods to upgrade the enantiopurity of 1 have been reported (9).…”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, 1 has been used as an intermediate in the preparation of pharmaceutical agents in a wide variety of therapeutic areas such as HIV protease inhibitors (2), immunosuppression (3), and oncology (4). A number of approaches to the synthesis of enantiomerically enriched 1 based on the use of a chiral auxiliary (5), chiral-pool starting materials (6,7), and resolution have been reported (8)(9)(10)(11)(12). However, these all suffer from factors, such as lengthy synthetic sequences or a maximum theoretical yield of 50%, making them less than ideal approaches from an industrial perspective.…”

mentioning

confidence: 99%

An efficient, palladium-catalyzed, enantioselective synthesis of (2 R )-3-butene-1,2-diol and its use in highly selective Heck reactions

Cheeseman

Fox

Jackson

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

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A robust and scalable procedure for the palladium-catalyzed dynamic kinetic asymmetric transformation of 3,4-epoxy-1-butene into (2R)-3-butene-1,2-diol with water as the cosolvent is reported. Examination of the effects of solvent and temperature led to the identification of conditions that permitted use of 0.025 mol % catalyst, providing (2R)-3-butene-1,2-diol in 84% isolated yield and 85% enantiomeric excess. Subsequent Heck reactions with a diverse range of coupling partners are described and the influence of their electronic nature on maintaining the enantiopurity of the diol is discussed. E nhanced drug efficacy, more economic use of resources, and, above all else, ever more stringent regulatory policies have all contributed to an increased demand from the pharmaceutical industry for single-enantiomer compounds. This has been a major driving force within the chemical community for the development of novel methods for the asymmetric synthesis of a myriad of chiral building blocks. Single-enantiomer vinylglycols, such as (2R)-3-butene-1,2-diol, (R)-1, are versatile polyfunctional chiral synthons that can be can be manipulated in a highly stereo-and chemoselective manner. The utility of 1, in particular, has been aptly demonstrated in the synthesis of a wide variety of chiral building blocks (1). Furthermore, 1 has been used as an intermediate in the preparation of pharmaceutical agents in a wide variety of therapeutic areas such as HIV protease inhibitors (2), immunosuppression (3), and oncology (4). A number of approaches to the synthesis of enantiomerically enriched 1 based on the use of a chiral auxiliary (5), chiral-pool starting materials (6, 7), and resolution have been reported (8)(9)(10)(11)(12). However, these all suffer from factors, such as lengthy synthetic sequences or a maximum theoretical yield of 50%, making them less than ideal approaches from an industrial perspective.An alternative approach to enantiomerically enriched 1 that proceeded via asymmetric palladium-catalyzed hydrolysis of 3,4-epoxy-1-butene, 2, in which the ligand 3 was superior to ligand 4 (Fig. 1), was reported by Trost and McEachern (13). By taking advantage of the interconversion of the -allyl intermediates 5 and 6, and the chiral environment provided by the ligand-metal complex, a dynamic system is established that provides high-enantiopurity product from racemic starting material. For the diol 1 to be obtained, cocatalysis with alkylboranes was reported to be necessary, whereas in the absence of such species the cyclic carbonate 7 was the reaction product.The high synthetic and economic value of single-enantiomer 1 and the potential for its formation in high yield by using a catalytic system led us to evaluate this method for its application on an industrial scale. In this article, we report our early-phase developmental work on this reaction, which led to a highly efficient, scalable, and robust modified route to 1. Along with this development, we also report subsequent selective Heck reactions of (R)-1. The Heck reaction...

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“…1:1 mixture of (S)-2-hydroxy-3-butenyl tosylate (S-3, >95% ee) and (R)-2-acetoxy-3-butenyl tosylate (R-4, >95% ee, 185.55 g, combined 0.70 mol maximum) from an enzymatic esterification resolution reaction 13 The initial filtrate and wash were stripped to afford 123.97 g of R-4 and S-3 in about a 75:25 ratio, respectively. This material can be freed of 3 by the selective reaction of the secondary hydroxyl with succinic anhydride and extractive removal of the resulting succinate half ester.…”

Section: (S)-2-hydroxy-3-butenyl Tosylate (S-3)mentioning

confidence: 99%

“…The primary monotosylate of 3-butene-1,2-diol (3) is of interest as an alternative source for these enantiomerically enriched products, as it can be envisioned as a precursor of both 3-butene-1,2-diol (1) and 3,4-epoxy-1-butene (2). Tosylate 3 can be readily prepared in high enantiomeric purity by either enzymatic 13 or chemical (Sharpless epoxidation) resolution processes. 14 Enantiomerically enriched 3 is one of the very few derivatives of 3-butene-1,2-diol that we have been able to crystallize to enantiomeric purity.…”

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confidence: 99%

The Preparation of Enantiomerically Pure 3,4-Epoxy-1-butene and 3-Butene-1,2-diol

Boaz¹,

Falling²,

Moore³

2005

Synlett

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Amine assisted enzymatic esterification of 1,2-diol monotosylates

Cited by 25 publications

References 5 publications

Characterization of an Indole-3-Acetamide Hydrolase from Alcaligenes faecalis subsp. parafaecalis and Its Application in Efficient Preparation of Both Enantiomers of Chiral Building Block 2,3-Dihydro-1,4-Benzodioxin-2-Carboxylic Acid

Characterization of an Indole-3-Acetamide Hydrolase from Alcaligenes faecalis subsp. parafaecalis and Its Application in Efficient Preparation of Both Enantiomers of Chiral Building Block 2,3-Dihydro-1,4-Benzodioxin-2-Carboxylic Acid

An efficient, palladium-catalyzed, enantioselective synthesis of (2 R )-3-butene-1,2-diol and its use in highly selective Heck reactions

The Preparation of Enantiomerically Pure 3,4-Epoxy-1-butene and 3-Butene-1,2-diol

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