Diversity‐Orientated Stereoselective Synthesis through Pd‐Catalyzed Switchable Decarboxylative C−N/C−S Bond Formation in Allylic Surrogates

Chemistry - A European Journal, Journal Year: 2018, Volume and Issue: 24(72), P. 19156 - 19161

Published: Oct. 25, 2018

Switchable catalytic transformation of reactants can be a powerful approach towards diversity-orientated synthesis from easily available molecular synthons. Herein, an endogenous ligand-controlled, Pd-catalyzed allylic substitution allowing for either selective C-N or C-S bond formation using vinylethylene carbonates (VECs) and N-sulfonylhydrazones as coupling partners has been developed. This versatile methodology provides facile, divergent route the highly chemo- stereoselective functional sulfones sulfonohydrazides. The newly developed protocol features wide substrate scope (nearly 80 examples), broad group tolerance, potential late-stage functionalization bioactive compounds. isolation crystallographic analysis catalytically competent π-allyl Pd complex suggests that pathway leading to products proceeds through different manifold previously proposed VECs with nucleophiles.

Language: Английский

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Catalytic Asymmetric Conjugate Addition of a Borylalkyl Copper Complex for Chiral Organoboronate Synthesis

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(50), P. 18131 - 18135

Published: Sept. 4, 2019

We report the catalytic enantioselective conjugate addition of a borylalkyl copper nucleophile generated in situ from 1,1-diborylmethane derivative to α,β-unsaturated diesters. In presence chiral N-heterocyclic carbene (NHC)-copper catalyst, this method facilitated incorporation CH2 Bpin moiety at β-position diesters yield β-chiral alkyl boronates up 86 % with high enantioselectivity. The alkylboron resulting diester products was converted into various functional groups by organic transformation C-B bond.

Language: Английский

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Selective C−C Coupling of Vinyl Epoxides with Diborylmethide Lithium Salts

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 25(34), P. 8013 - 8017

Published: April 24, 2019

Vinyl epoxides and styrene oxide can react with diborylmethide lithium salts through an exclusive SN 2 borylmethylation/ring opening in a regio- diastereoselective way, depending on the nature of substrate. The ring-opening protocol provides homoallylboronates that be transformed into challenging diastereomeric bishomoallylic alicyclic 1,3-diols. Unprecedented 3-borylated 1,2-oxaborolan-2-ol products were prepared by 2-methyl-2-vinyloxirane followed intramolecular cyclization.

Language: Английский

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Pd/Cu-Catalyzed Domino Cyclization/Deborylation of Alkene-Tethered Carbamoyl Chloride and 1,1-Diborylmethane

Organic Letters, Journal Year: 2020, Volume and Issue: 22(16), P. 6376 - 6381

Published: Aug. 5, 2020

Reported herein is a palladium/copper cooperative-catalyzed dicarbofunctionalization of alkene-tethered carbamoyl chlorides with 1,1-diborylmethane. This cyclization/deborylation cascade strategy allows for the expedient formation versatile borylated 3,3-disubstituted oxindole skeleton, allowing further functionalization via derivatization carbon-boron bond.

Language: Английский

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Palladium-Catalyzed [5 + 2] Annulation of Vinylethylene Carbonates with Barbiturate-Derived Alkenes

Organic Letters, Journal Year: 2020, Volume and Issue: 22(18), P. 7158 - 7163

Published: Sept. 3, 2020

A palladium/XantPhos-catalyzed [5 + 2] annulation of VECs with electron-deficient alkenes having an isolated carbon–carbon double bond has been developed to afford spirobarbiturate-tetrahydrooxepines. This study provides expedient assembly biologically interesting The easy scalability and versatile transformability the reaction products were also exhibited.

Language: Английский

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