Asymmetric synthesis of chiral tertiary borylated phosphonates by copper-catalyzed conjugate borylation

Kim, Jiwon; Lee, Hyesu; Yun, Jaesook

doi:10.1016/j.tet.2019.04.010

Cited by 5 publications

(3 citation statements)

References 26 publications

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“…β-Borylation of α,β-unsaturated carbonyl and related compounds continues to be an active area of research (Scheme a). , Ferrocenyl-type ligands such as Josiphos and Taniaphos are particularly efficient for controlling the enantioselectivity of these transformations (Scheme b). ,, For example, Whiting and co-workers expanded on their previous work and demonstrated ligand-controlled sequential asymmetric protoborations leading to syn - or anti -diboryl esters to access chiral syn - and anti -1,3-diol derivatives (Scheme c) wherein Josiphos ligands enabled the effect of the existing chiral center to be overridden. Likewise, catalytic asymmetric conjugate 1,6-, 1,8-, and 1,10-borylations using Josiphos ligands afford α-chiral boronates with high enantioselectivity .…”

Section: Copper-catalyzed C–b Bond Formationmentioning

confidence: 99%

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

et al. 2021

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Organoboron reagents represent a unique class of compounds because of their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation of the carbon−boron bond into a carbon−X (X = C, N, and O) bond in a stereocontrolled fashion has become invaluable in medicinal chemistry, agrochemistry, and natural products chemistry as well as materials science. Over the past decade, first-row dblock transition metals have become increasingly widely used as catalysts for the formation of a carbon−boron bond, a transformation traditionally catalyzed by expensive precious metals. This recent focus on alternative transition metals has enabled growth in fundamental methods in organoboron chemistry. This review surveys the current state-of-the-art in the use of first-row d-block element-based catalysts for the formation of carbon−boron bonds.

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Section: Copper-catalyzed C–b Bond Formationmentioning

confidence: 99%

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

et al. 2021

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“…In 2015, Feringa and co-workers have reported the first copper-catalyzed asymmetric β-borylation of α,β-unsaturated phosphine oxides, affording optically active organoboronate esters in good yields with high enantiomeric excess (Scheme a) . Later, Yun and co-workers synthesized chiral tertiary borylated phosphonates by copper-catalyzed asymmetric conjugate borylation . Takacs and co-workers developed the rhodium-catalyzed asymmetric β- and γ-borylation of allylic phosphonates .…”

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Copper-Catalyzed Asymmetric Boroprotonation of Phosphinylallenes

Cheng

et al. 2023

Org. Lett.

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Synthesis of chiral phosphorus compounds from readily available substrates by a facile method is an attractive strategy. In this study, an efficient route for copper-catalyzed asymmetric boroprotonation of phosphinylallenes with bis(pinacolato)diboron with high regioselectivity was developed, affording chiral allylphosphine oxides in high yields with high enantioselectivities of up to 98% ee. The synthetic utility was further demonstrated by the facile transformation of the chiral allylphosphine oxides to several stereospecific products.

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“…1 Transition-metal-catalyzed conjugate borylations of electron deficient alkenes have proven to be a robust strategy to access complex boronic esters using bis(pinacolato)diboron (B 2 pin 2 ). 2 The use of Cu(I) salts and chiral phosphine-or NHC-type ligands has enabled the asymmetric -borylation of ,-unsaturated esters, 3 ketones, 3a,4 amides, 5 sulfones, 6 phosphonates, 7 and phosphine oxides (Scheme 1). 8 However, no such functionalization of related ,-unsaturated acyl silanes has yet been described.…”

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confidence: 99%

Asymmetric Cu(I)-Catalyzed Conjugate Borylation of α,β-Unsaturated Acyl Silanes

Rousseaux,

Palermo,

Imbriaco

et al. 2023

Synlett

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We report the development of a Cu(I)-catalyzed conjugate borylation of α,β-unsaturated acyl silanes using bis(pinacoloto)diboron. Racemic borylations of β-aryl- and β-alkyl-substituted silyl enones were achieved using ligand-free conditions to access β-borylated acyl silanes in up to 97% yield. Josiphos enabled the synthesis of enantioenriched boronic esters in up to 58% yield and 94% ee. The racemic reaction was demonstrated on 5.0 mmol scale and isolation of the boronic esters was achieved using simple filtration and normal-phase chromatography. This work supplements known methods to access boronic esters from electron-deficient olefins using Cu(I) catalysis.

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Asymmetric synthesis of chiral tertiary borylated phosphonates by copper-catalyzed conjugate borylation

Cited by 5 publications

References 26 publications

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Copper-Catalyzed Asymmetric Boroprotonation of Phosphinylallenes

Asymmetric Cu(I)-Catalyzed Conjugate Borylation of α,β-Unsaturated Acyl Silanes

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