Iridium‐Catalyzed Distal Hydroboration of Aliphatic Internal Alkenes

Wang, Guangzhu; Liang, Xinyi; Chen, Lili; Gao, Qian; Wang, Jianguo; Zhang, Panke; Peng, Qian; Xu, Senmiao

doi:10.1002/anie.201902464

Cited by 34 publications

(10 citation statements)

References 78 publications

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“…However, the metal-catalyzed hydroboration of aryl-substituted alkenes gave the reverse Markovnikov regioselectivity with catecholborane (HBcat) or pinacolborane (HBpin) as hydrogen and boron sources, mainly because of the electronic bias of the vinyl group (Scheme b(i)) . Furthermore, the regiospecific hydroboration of internal alkenes was achieved through the introduction of directing groups or remote electronic effects in alkene substrates (Scheme b(ii)). Despite these results, Markovnikov hydroboration of aliphatic terminal alkenes that can be obtained from petrochemical feedstock or synthesized in a straightforward manner remain elusive.…”

Section: Introductionmentioning

confidence: 99%

Ligand-Free Iron-Catalyzed Regioselectivity-Controlled Hydroboration of Aliphatic Terminal Alkenes

Qiao

Jiang

et al. 2020

ACS Catal.

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The control of regioselectivities has been recognized as the elementary issue for alkene hydroboration. Despite considerable progress, the specificity of alkene substrates or the adjustment of ligands was necessary for specific regioselectivities, which restrict the universality and practicability. Herein, we report a ligand-free iron-catalyzed regiodivergent hydroboration of aliphatic terminal alkenes that obtains both Markovnikov and anti-Markovnikov hydroboration products in high regioselectivities. Notably, solvents and bases were shown to be crucial factors influencing the regioselectivities and further studies suggested that the iron–boron alkoxide ate complex is the key intermediate that determines the unusual Markovnikov regioselectivity. Terminal alkenes with diverse structures (monosubstituted and 1,1-disubstituted, open-chain and exocyclic) underwent the transformation smoothly. The reaction does not require the addition of auxiliary ligands and it can be performed on a gram scale, thus providing an efficient and sustainable method for the synthesis of primary, secondary, and tertiary alkyl borates.

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Section: Introductionmentioning

confidence: 99%

Ligand-Free Iron-Catalyzed Regioselectivity-Controlled Hydroboration of Aliphatic Terminal Alkenes

Qiao

Jiang

et al. 2020

ACS Catal.

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“…1A ). 6 The coordination of directing groups with the TM catalysts can deliver hydroboration products with controllable distal 7 and/or proximal 8 selectivity. Recently, directed borylation of aliphatic C–H bonds with proximal 9 and distal 10 selectivity has also gained momentum.…”

Section: Introductionmentioning

confidence: 99%

Rhodium-catalysed selective C–C bond activation and borylation of cyclopropanes

et al. 2021

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“…However, the regiodivergent and enantioselective hydroboration of enamides faces several challenges. First, current enantioselective hydroborations are mostly limited to terminal alkenes, styrenes, and internal alkenes with a coordinating group . Catalytic asymmetric hydroboration of electron-rich olefins is rare. , Highly enantioselective hydroboration of multisubstituted enamides with hydroborane is unknown .…”

Section: Introductionmentioning

confidence: 99%

Rhodium-Catalyzed Regiodivergent and Enantioselective Hydroboration of Enamides

et al. 2019

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Chiral α- and β-aminoboronic acids exhibit unique biological activities. General methods for the synthesis of these bioisosteres of amino acids are highly desirable. We report a facile preparation of these compounds through rhodium-catalyzed regiodivergent and enantioselective hydroboration of enamides. Catalytic asymmetric synthesis of α- and β-aminoboronic esters with high regio-, diastereo-, and enantioselectivities were achieved through effective catalyst control and tuning substrate geometry. Starting from easily available materials, this strategy provides a unified synthetic access to both enantioenriched α-boration and β-boration products. The synthetic utility of these methods was demonstrated by efficient synthesis of an anticancer drug molecule and diverse transformations of the boration products.

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Iridium‐Catalyzed Distal Hydroboration of Aliphatic Internal Alkenes

Abstract: Scheme 1. Transition-metal-catalyzed regioselective hydroboration of aliphatic internal alkenes.D G= directing group.

Cited by 34 publications

References 78 publications

Ligand-Free Iron-Catalyzed Regioselectivity-Controlled Hydroboration of Aliphatic Terminal Alkenes

Ligand-Free Iron-Catalyzed Regioselectivity-Controlled Hydroboration of Aliphatic Terminal Alkenes

Rhodium-catalysed selective C–C bond activation and borylation of cyclopropanes

Rhodium-Catalyzed Regiodivergent and Enantioselective Hydroboration of Enamides

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