Synthesis and properties of pinanediol .alpha.-amido boronic esters

Matteson, Donald S.; Jesthi, Pradipta K.; Sadhu, Kizhakethil Mathew

doi:10.1021/om00086a024

Cited by 92 publications

(67 citation statements)

References 2 publications

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“…(α-Chloroalkyl)-boronic ester 118 was made in the usual way and the reaction with lithiohexamethyldisilazane was carried out under typical conditions for nucleophilic substitution of chloro boronic esters to form silylated amino boronic ester 119. Desilylation and acylation to 120 were first carried out by adding a mixture of acetic acid and acetic anhydride, though it was soon found that desilylation with one equivalent of methanol yielded an intermediate that could be acylated with benzyloxycarbonyl chloride or other acylating agents [64]. At the time of these reports, the only known way to remove pinanediol from its boronic esters was treatment with boron trichloride, which degraded the pinanediol to black tar and destroyed the carbobenzyloxy substituent, though it left acetamido groups intact.…”

Section: Amino and Amido Substituentsmentioning

confidence: 99%

“…Several additional [α-(bistrimethylsilylamino)alkyl]boronic and derived (α-acetamidoalkyl)boronic esters were synthesized in early work [64,65]. Pinanediol (R)-(bis-1-trimethylsilylamino-3-methylbutyl)boronate (123) has subsequently proved to be the most important synthetic intermediate to date of this series for pharmaceutical purposes.…”

Section: Boronic Ester Intermediates In Synthesismentioning

confidence: 99%

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(α‐Haloalkyl)boronic Esters in Asymmetric Synthesis

Matteson¹

2005

Boronic Acids

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The utility of (α-haloalkyl)boronic esters in asymmetric synthesis results from a unique combination of several features of their chemistry. A wide variety of products can be obtained in very high stereopurity, and the reactions are compatible with a considerable variety of functional substituents, provided that OH and NH groups are masked. Stereospecific displacement of halide from an (α-haloalkyl)boronic ester with a nucleophile yields an asymmetric boronic ester, which can either be converted stereospecifically into another product such as an alcohol or put into another cycle of reaction with (dihalomethyl)lithium to install additional stereocenters. The general synthetic utility of these boronic esters can best be understood from a detailed outline of the general processes involved.The most useful biological applications of these compounds have included the synthesis of some asymmetric insect pheromones in very high stereopurity, described in Sections 8.3.1 and 8.3.3, and the proteasome inhibitor "Velcade™" (bortezomib) developed by Millennium Pharmaceuticals and recently approved by the United States FDA as well as the European Union for treatment of relapsed and refractory multiple myeloma, Section 8.3.6. General Description of (α-Haloalkyl)boronic Ester Chemistry A Brief History of Boronic Ester ChemistryFirst, simple achiral boronic acids and esters are readily available from various sources (Chapter 1). The first synthesis from an organozinc reagent preceded general acceptance of Avogadro's hypothesis [1], and was superseded nearly a century ago by the now standard preparation from Grignard reagents [2,3]. Hydroboration has Boronic Acids. Edited by Dennis G. Hall

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Section: Amino and Amido Substituentsmentioning

confidence: 99%

Section: Boronic Ester Intermediates In Synthesismentioning

confidence: 99%

(α‐Haloalkyl)boronic Esters in Asymmetric Synthesis

Matteson¹

2005

Boronic Acids

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“…We have previously reported [2-(benzyloxy)-1-chloroethyl]boronic esters [3,11,12]. Earlier attempts to convert these to [2-(benzyloxy)-1-[bis(trimethylsilyl)amino]ethyl]boronic esters and react them with (dichloromethyl)lithium failed.…”

Section: Protected [1-amino-2-(trityloxy)ethyl]boronic Estersmentioning

confidence: 99%

An Exploratory Study of Silylated Amino Boronic Ester Chemistry

et al. 1997

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“…This enabled the synthesis of many potent boronic acid-based enzyme inhibitors. Thereafter, several variations of the general route have been developed and used for these synthesis of different kinds of enzyme inhibitors [13][14][15][16][17]. The development of the synthetic methodologies is discussed in detail in Chapter 8, and therefore will not be duplicated here.…”

Section: Introductionmentioning

confidence: 99%

“…15 Fluorescent labeling studies of sLex expressing HEPG2 cells (left) and non-expressing COS7 cells (right) with compound 64e (1 µM).…”

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confidence: 99%