Stereoselective synthesis of functionalised triol units by SnCl4 promoted allylation of α-benzyloxyaldehydes: crucial role of the stoichiometry of the Lewis acid

Dubost, Christophe; Leroy, B.; Markó, István E.; Tinant, Bernard; Declercq, Jean‐Paul; Bryans, Justin S.

doi:10.1016/j.tet.2004.06.084

Cited by 24 publications

(11 citation statements)

References 38 publications

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“…We have not observed any racemization nor epimerization in the products. 22 However, in the particular case of citronellol, during the course of the esterification reaction, migration of a double bond took place. This is most likely due to the reversible addition–elimination of hydrochloride and is not hampered by the addition of the base.…”

Section: Resultsmentioning

confidence: 99%

“…[α] D 20 +5 (c 2.32, CHCl 3 ). 1 H NMR (300 MHz, CDCl 3 ) δ 7.30− 7.20 (m, 15H), 5.04 (h,J = 6.3 Hz,1H),2H), 1.18− 1.04 (m, 2H), 1.17 (d,J = 6.3 Hz,3H),0.79 (t,J = 7.3 Hz,3H). 13 C{ 1 H} NMR (75 MHz, CDCl 3 ) δ 173.…”

Section: ■ Conclusionmentioning

confidence: 99%

“…As early as in 1912, Chugayev reported the optical rotation of menthyl triphenylacetate, the first chiral ester derivative of triphenylacetic acid . However, neither this nor the later works contributed much to understanding the mechanism of inducing the optical activity in such compounds . Thus, being for ages isolated curiosities of chemistry, the chiral mono- and diesters of triphenylacetic acid constitute the missing pieces of the jigsaw puzzle showing dynamic stereochemistry of trityl-containing compounds.…”

Section: Introductionmentioning

confidence: 99%

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Chiral Triphenylacetic Acid Esters: Residual Stereoisomerism and Solid-State Variability of Molecular Architectures

2021

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We have proven the usability and versatility of chiral triphenylacetic acid esters, compounds of high structural diversity, as chirality-sensing stereodynamic probes and as molecular tectons in crystal engineering. The low energy barrier to stereoisomer interconversion has been exploited to sense the chirality of an alkyl substituent in the esters. The structural information are cascaded from the permanently chiral alcohol (inducer) to the stereodynamic chromophoric probe through cooperative interactions. The ECD spectra of triphenylacetic acid esters are highly sensitive to very small structural differences in the inducer core. The tendencies to maximize the C–H···O hydrogen bonds, van der Waals interactions, and London dispersion forces determine the way of packing molecules in the crystal lattice. The phenyl embraces of trityl groups allowed, to some extent, the control of molecular organization in the crystal. However, the spectrum of possible molecular arrangements is very broad and depends on the type of substituent, the optical purity of the sample, and the presence of a second trityl group in the proximity. Racemates crystallize as the solid solution of enantiomers, where the trityl group acts as a protecting group for the stereogenic center. Therefore, the absolute configuration of the inducer is irrelevant to the packing mode of molecules in the crystal.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Conclusionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Chiral Triphenylacetic Acid Esters: Residual Stereoisomerism and Solid-State Variability of Molecular Architectures

2021

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“…The latter turned out to be the best choice, especially because it allowed the preservation of the integrity of the sensitive lactate stereogenic center. The corresponding CH arylation precursor 7 was synthesized in three steps from commercially available methyl D ‐lactate 11 (Scheme ) 23. Of note, directed C(sp 3 )H arylation is known to give rise to various byproducts such as polyarylated compounds, thereby complicating purification and up‐scaling 12–13.…”

Section: Resultsmentioning

confidence: 99%

“…The corresponding CÀHa rylation precursor 7 was synthesized in three steps from commercially availablem ethyl d-lactate 11 (Scheme 6). [23] Of note, directed C(sp 3 )ÀHa rylation is known to give rise to various byproducts such as polyarylatedc ompounds, therebyc omplicating purification and up-scaling. [12][13] We thus performed the reactionoptimization with the main objective to devise ap ractical, scalable process ( Table 5).…”

Section: Synthesis Of the Hpla Fragmentsmentioning

confidence: 99%

Divergent Synthesis of Aeruginosins Based on a C(sp³)H Activation Strategy

Dailler

Danoun

Ourri

et al. 2015

Chemistry A European J

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A general and scalable access to the aeruginosin family of marine natural products, exhibiting potent inhibitory activity against serine proteases, is reported. This was enabled by the strategic use of two recently implemented Pd-catalyzed C(sp(3))-H activation reactions. The first method allowed us to obtain the common 2-carboxy-6-hydroxyoctahydroindole (Choi) core of the target molecules on a large scale, whereas the second method provided a rapid and divergent access to various hydroxyphenyllactic (Hpla) subunits, including halogenated ones. This unique strategy, together with an optimization of the fragment coupling sequence allowed the synthesis of four aeruginosins, that is, 98A-C and 298A from the chiral pool. Among them, aeruginosin 298A was synthesized on an unprecedentedly large scale. In addition, halogenated aeruginosins 98A and 98C were synthesized for the first time, thanks to a fine-tuning of the final hydrogenation step.

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Gold‐Catalyzed Imination/Mannich Reaction Cascades of 3‐En‐1‐ynamides with Anilines and Aldehydes to Enable 1,5‐Nitrogen Functionalizations

Singh

Liu

2016

Adv Synth Catal

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Gold-catalyzed imination/Mannich reaction cascadeso nr eadily available 3-en-1-ynamides enable the diastereoselectives ynthesis of 1,5-iminoamino compounds in ao ne-pot operation. The reactions workw ell with diversified3 -en-1-ynamides,a ldehydes anda nilines with good to excellent diastereoselectivities.O ur control experiments indicate gold-catalyzed aminations of 3-en-1-ynamides to yield a-imino allylgold intermediates that react subsequently with iminiums to implement the Mannich reactions stereoselectively.T he reactions proceed with anti-selectivity for those 3-en-1-ynamides bearing acyclic alkenes whereas syn-selectivity is seen for theirc ycloalkene-baseda nalogues.A n open-transition state can satisfactorily rationalize these observeds tereoselectivities based on an antiperiplanar conformation.

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Stereoselective synthesis of functionalised triol units by SnCl4 promoted allylation of α-benzyloxyaldehydes: crucial role of the stoichiometry of the Lewis acid

Cited by 24 publications

References 38 publications

Chiral Triphenylacetic Acid Esters: Residual Stereoisomerism and Solid-State Variability of Molecular Architectures

Chiral Triphenylacetic Acid Esters: Residual Stereoisomerism and Solid-State Variability of Molecular Architectures

Divergent Synthesis of Aeruginosins Based on a C(sp³)H Activation Strategy

Gold‐Catalyzed Imination/Mannich Reaction Cascades of 3‐En‐1‐ynamides with Anilines and Aldehydes to Enable 1,5‐Nitrogen Functionalizations

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Stereoselective synthesis of functionalised triol units by SnCl4 promoted allylation of α-benzyloxyaldehydes: crucial role of the stoichiometry of the Lewis acid

Cited by 24 publications

References 38 publications

Chiral Triphenylacetic Acid Esters: Residual Stereoisomerism and Solid-State Variability of Molecular Architectures

Chiral Triphenylacetic Acid Esters: Residual Stereoisomerism and Solid-State Variability of Molecular Architectures

Divergent Synthesis of Aeruginosins Based on a C(sp3)H Activation Strategy

Gold‐Catalyzed Imination/Mannich Reaction Cascades of 3‐En‐1‐ynamides with Anilines and Aldehydes to Enable 1,5‐Nitrogen Functionalizations

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Divergent Synthesis of Aeruginosins Based on a C(sp³)H Activation Strategy