Stereoselective Total Synthesis of (+)‐Giganin and Its C10 Epimer by Using Late‐Stage Lithiation–Borylation Methodology

Fletcher, Catherine J.; Wheelhouse, Katherine M. P.; Aggarwal, Varinder K.

doi:10.1002/ange.201208403

Cited by 12 publications

(2 citation statements)

References 69 publications

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“…The latter method is more direct and more versatile as it enables ready access to alternative stereoisomers. We (and others 15 , 16 , 17 , 18 ) have focussed on reagent-controlled methodology and we have found that Hoppe’s lithiated carbamate 19 , 20 , 21 homologate boronic esters with high stereocontrol and have applied this methodology in the synthesis of a number of natural products 22 , 23 , 24 , 25 , 26 . In order to apply this methodology to iterative homologations we set the goal of creating a carbon chain with 10 contiguous methyl substituents with total stereocontrol ( Figure 1b ).…”

Section: Development Of the Iterative Homologation Processmentioning

confidence: 98%

Assembly-line synthesis of organic molecules with tailored shapes

Burns

Essafi

Bame

et al. 2014

Nature

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279

157

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Molecular assembly lines, where molecules undergo iterative processes involving chain elongation and functional group manipulation are hallmarks of many processes found in Nature. We have sought to emulate Nature in the development of our own molecular assembly line through iterative homologations of boronic esters. Here we report a reagent (α-lithioethyl triispopropylbenzoate) which inserts into carbon-boron bonds with exceptionally high fidelity and stereocontrol. Through repeated iteration we have converted a simple boronic ester into a complex molecule (a carbon chain with ten contiguous methyl groups) with remarkably high precision over its length, its stereochemistry and therefore its shape. Different stereoisomers were targeted and it was found that they adopted different shapes (helical/linear) according to their stereochemistry. This work should now enable scientists to rationally design and create molecules with predictable shape, which could have an impact in all areas of molecular sciences where bespoke molecules are required.

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Section: Development Of the Iterative Homologation Processmentioning

confidence: 98%

Assembly-line synthesis of organic molecules with tailored shapes

Burns

Essafi

Bame

et al. 2014

Nature

Self Cite

279

157

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“…The possibility of diastereomer differentiation by NMR spectroscopy generally depends on the number of bonds between the chiral centers. 34,35 The selectivity for 13 C nuclei is usually much higher than for 1 H. The sensitivity of both 1 H and 13 C NMR in the analysis of different impurities has often been underestimated. However, recently an interesting work has been published reporting a highly efficient and environmentally benign procedure for fast NMR analysis of small samples of chiral alcohols and amines.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Quantitative Analysis of Diastereomeric Linked Ester Conjugates With Remote Stereocenters Using High‐Field NMR and Chiral HPLC

et al. 2013

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A stereochemically safe high-yielding procedure for linking unprotected as well as protected hydroxycarboxylic acids to chiral secondary alcohols via glycolic acid linker is proposed. L-menthol has been linked with both enantiomers of mandelic, malic, and methoxyphenylacetic acid using bromo- or iodoacetyl group as a precursor of the glycolic acid linker. High-field nuclear magnetic resonance (NMR) and chiral high-performance liquid chromatography (HPLC) determination of high diastereomeric ratio (dr) (>99%) of the products bearing remote stereocenters was explored. Chiral HPLC allowed quantitation of the diastereomers up to dr 99.9/0.1. High-field NMR quantitation of the diastereomeric and parent alcoholic impurities in esters was demonstrated at the molar 0.3% and 0.03% levels, respectively. These analyses were done via comparison of integral intensities from major component (13)C satellites in (1)H or even in (13)C spectra to the (1)H or (13C signals of impurities. Despite lower sensitivity, the last option generally has much better selectivity. In this way the dynamic resolution is brought down by two orders.

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Synthesis of 2‐Aryl‐1,3‐Cyclopentanediones through Catalytic Borylation as a Key Step

Palau‐Lluch

Fernández

2015

Asian J Org Chem

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We describe ap ractical straightforward synthesis of 2-aryl-1,3-cyclopentanediones from a-iodoenones, via in situ palladium-catalyzed cross-couplingw ith hindereda rylboronic acids followed by copper-mediated b-borylation and finishing with an oxidative work-up. The sequential reactions are performed without intermediate isolation and the whole synthetic strategy might become of practical use fort he major challenges that companies currently face in R&D in agrochemicals.

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Stereoselective Total Synthesis of (+)‐Giganin and Its C10 Epimer by Using Late‐Stage Lithiation–Borylation Methodology

Cited by 12 publications

References 69 publications

Assembly-line synthesis of organic molecules with tailored shapes

Assembly-line synthesis of organic molecules with tailored shapes

Synthesis and Quantitative Analysis of Diastereomeric Linked Ester Conjugates With Remote Stereocenters Using High‐Field NMR and Chiral HPLC

Synthesis of 2‐Aryl‐1,3‐Cyclopentanediones through Catalytic Borylation as a Key Step

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