Part 2. Mechanistic aspects of the reduction of <i>S</i>-alkyl-thionocarbonates in the presence of triethylborane and air

Allais, Florent; Boivin, Jean; Nguyen, Van Tai

doi:10.1186/1860-5397-3-46

Cited by 23 publications

(11 citation statements)

References 11 publications

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“…18 The reaction of amino acid derivative xanthate 20 with CD 3 OD using Et 3 B/O 2 initiation provides deuterated product 30 in good yield (71%, 85% deuterium incorporation). 19 Thus, the xanthylation-deuteration sequence constitutes a formal, site-selective monodeuteration of aliphatic C–H bonds, which, to our knowledge, does not exist.…”

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confidence: 96%

“…Such a process would expedite the preparation of isotopically labeled compounds for mechanistic and metabolic studies and offer an attractive route to deuterated drugs with enhanced pharmacokinetic properties . The reaction of amino acid derivative xanthate 20 with CD 3 OD using Et 3 B/O 2 initiation provides deuterated product 30 in good yield (71%, 85% deuterium incorporation) . Thus, the xanthylation–deuteration sequence constitutes a formal, site-selective monodeuteration of aliphatic C–H bonds, which, to our knowledge, does not exist.…”

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confidence: 99%

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C–H Xanthylation: A Synthetic Platform for Alkane Functionalization

2016

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Intermolecular functionalizations of aliphatic C–H bonds offer unique strategies for the synthesis and late-stage derivatization of complex molecules, but the chemical space accessible remains limited. Herein, we report a transformation significantly expanding the chemotypes accessible via C–H functionalization. The C–H xanthylation proceeds in useful chemical yields with the substrate as limiting reagent using blue LEDs and an easily prepared N-xanthylamide. The late-stage functionalizations of complex molecules occur with high levels of site selectivity, and a variety of common functionality is tolerated in the reaction. This approach capitalizes on the versatility of the xanthate functional group via both polar and radical manifolds to unlock a wide array of C–H transformations previously inaccessible in synthesis.

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confidence: 96%

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confidence: 99%

C–H Xanthylation: A Synthetic Platform for Alkane Functionalization

2016

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“…Reagents based on O À Hh ydrogen donors such as alcohols and water are particularly attractive owing to their availability,l ow toxicity,a nd low price,b ut they need to be activated to become hydrogen atom donors.U pon complexation with ab oron Lewis acid such as trimethyl-and triethylborane [12] the OÀHb onds of water and alcohols is considerably weakened, [13] and such complexes have been used in radical-mediated deoxygenation and deiodination reactions. [12a,b,14] However,t his approach gives rise to Hdonors that are about two orders of magnitude less potent than tin hydride derivatives.…”

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Catechols as Sources of Hydrogen Atoms in Radical Deiodination and Related Reactions

et al. 2016

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When used with trialkylboranes, catechol derivatives, which are low-cost and low toxicity, are valuable hydrogen atom donors for radical chain reactions involving alkyl iodides and related radical precursors. The system 4-tert-butylcatechol/triethylborane has been used to reduce a series of secondary and tertiary iodides, a xanthate, and a thiohydroxamate ester. Catechol derivatives are right in the optimal kinetic window for synthetic applications, as demonstrated by highly efficient radical cyclizations. Cyclizations leading to the formation of quaternary centers can be performed in an all-at-once process (no slow addition of the hydrogen atom donor) at standard concentrations. The H-donor properties of catechol derivatives can be fine-tuned by changing their substitution pattern. In slow radical cyclization processes, an enhanced ratio of cyclized/uncyclized products was obtained by using 3-methoxycatechol instead of 4-tert-butylcatechol.

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“…Other reagents used were hypophosphorous acid and triethylamine with 1,1′-azobis(cyclohexanecarbonitrile) (H 3 PO 2 -Et 3 N-ACCN), 133 triethylborane and air 134,135 and tetrabutylammonium peroxydisulfate [(Bu 4 N) 2 S 2 O 8 ] with NaHCO 3 . 85,136…”

Section: Deoxygenation Methodsmentioning

confidence: 99%