Transition‐Metal‐Free Cross‐Coupling by Using Tertiary Benzylic Organoboronates

Takeda, Masatoshi; Nagao, Kazunori; Ohmiya, Hirohisa

doi:10.1002/anie.202010251

Cited by 27 publications

(17 citation statements)

References 57 publications

(11 reference statements)

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“…Of note, the preparation of all-carbon quaternary carbon center are always big challenges in organic synthesis 42 , with our strategy, the quaternary carbon center could be built up conveniently. For instance, besides the simple tertiary aliphatic groups, such as tert- butyl ( 4a ), 3-methylpentyl ( 4b ) and 1-adamantyl ( 4c ), those ones bearing functional groups, like acetal ( 4d ) and ester ( 4e ), were also compatible in this transformation.…”

Section: Resultsmentioning

confidence: 99%

Photo-induced trifunctionalization of bromostyrenes via remote radical migration reactions of tetracoordinate boron species

Liao

Chen

et al. 2022

Nat Commun

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Tetracoordinate boron species have emerged as radical precursors via deboronation by photo-induced single electron transfer (SET) pathway. These reactions usually produce an alkyl radical and boron-bound species, and the valuable boron species are always discarded as a by-product. Given the importance of boron species, it will be very attractive if the two parts could be incorporated into the eventual products. Herein we report a photo-catalyzed strategy in which in situ generated tetracoordinated boron species decomposed into both alkyl radicals and boron species under visible light irradiation, due to the pre-installation of a vinyl group on the aromatic ring, the newly generated alkyl radical attacks the vinyl group while leaving the boron species on ipso-position, then both radical part and boron moiety are safely incorporated into the final product. Tertiary borons, secondary borons, gem-diborons as well as 1,2-diborons, and versatile electrophiles are all well tolerated under this transformation, of note, ortho-, meta- and para-bromostyrenes all demonstrated good capabilities. The reaction portraits high atom economy, broad substrate scope, and diversified valuable products with tertiary or quaternary carbon center generated, with diborons as substrates, Csp2-B and Csp3-B are established simultaneously, which are precious synthetic building blocks in chemical synthesis.

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Section: Resultsmentioning

confidence: 99%

Photo-induced trifunctionalization of bromostyrenes via remote radical migration reactions of tetracoordinate boron species

Liao

Chen

et al. 2022

Nat Commun

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“…Bpin group could also be converted to vinyl group with SiHPh 2 intact ( 3 a‐3 ). And 4 a could be utilized for transition‐metal‐free cross‐coupling to prepare tertiary benzylic silane ( 4 a‐3 ), [26] although, the yield was low due to the side reactions (deboration and desilylation). Meanwhile, Bpin group and Si−H bond could also be both converted in one‐pot reaction ( 2 a‐4 ).…”

Section: Resultsmentioning

confidence: 99%

Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

et al. 2021

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Regiodivergent addition reactions provide straightforward and atom‐economic approaches to access different regioisomers. However, the regio‐chemistry control to access all the possible results is still challenging especially for the reaction involving multiple addition steps. Herein, we reported regio‐controllable cobalt‐catalyzed sequential hydrosilylation/hydroboration of arylacetylenes, delivering all the possible regio‐outcomes with high regioselectivities (up to >20/1 rr for all the cases). Each regioisomer of value‐added silylboronates could be efficiently and regioselectively obtained from the same materials. The adjustment of the ligands of cobalt catalysts combined with dual catalysis relay strategy is the key to achieve regio‐chemistry control. This regio‐controllable research might inspire the exploration of the diversity‐oriented synthesis that involves multiple additions and provide full sets of regioisomers of other synthetic useful molecules.

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“…We sought a new benzylic arylation method that blends the modularity and selectivity of cross-coupling with the practicality of a base-promoted protocol. This drew our attention toward Lewis base activation of Lewis acidic benzyl compounds, an underdeveloped approach for aryl Csp 2 –Csp 3 coupling . In this regard, benzyltrimethylsilanes could be ideal coupling partners as they are air stable, nonhygroscopic, and easily accessed in great diversity .…”

mentioning

confidence: 99%

Lewis Basic Salt-Promoted Organosilane Coupling Reactions with Aromatic Electrophiles

Reidl

Bandar

2021

J. Am. Chem. Soc.

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Lewis basic salts promote benzyltrimethylsilane coupling with (hetero)aryl nitriles, sulfones, and chlorides as a new route to 1,1-diarylalkanes. This method combines the substrate modularity and selectivity characteristic of cross-coupling with the practicality of a base-promoted protocol. In addition, a Lewis base strategy enables a complementary scope to existing methods, employs stable and easily prepared organosilanes, and achieves selective arylation in the presence of acidic functional groups. The utility of this method is demonstrated by the synthesis of pharmaceutical analogues and its use in multicomponent reactions.

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Transition‐Metal‐Free Cross‐Coupling by Using Tertiary Benzylic Organoboronates

Cited by 27 publications

References 57 publications

Photo-induced trifunctionalization of bromostyrenes via remote radical migration reactions of tetracoordinate boron species

Photo-induced trifunctionalization of bromostyrenes via remote radical migration reactions of tetracoordinate boron species

Regio‐controllable Cobalt‐Catalyzed Sequential Hydrosilylation/Hydroboration of Arylacetylenes

Lewis Basic Salt-Promoted Organosilane Coupling Reactions with Aromatic Electrophiles

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