Generation and Application of (Diborylmethyl)zinc(II) Species: Access to Enantioenriched <i>gem</i>‐Diborylalkanes by an Asymmetric Allylic Substitution

Described herein is an asymmetric allylic aromatization (AAAr) strategy that employs readily accessible equivalents of benzylic nucleophiles in iridium-catalyzed allylic substitution reactions with the concomitant formation of aromatic rings by aromatization. The optimizedr eaction conditions involving ac atalyst derived from ac ommercially available iridium precursor and the Carreira ligand are compatible with equivalents of benzylic nucleophiles derived from 4-or 5-methyloxazoles,5 -methylthiazoles,4 -o r5methylfurans,2 -o r3 -methylbenzofurans,3 -methylbenzothiophene,3 -methylindole,1 -methylnaphthalene,a nd methylbenzene. This strategy provides straightforwarda ccesses to valuable heterocyclic aromatic compounds,b earing ah omobenzylic stereogenic center,inanenantiopure form and would be difficult to access otherwise.T he versatility of the reaction was showcased by the further elaboration of the products into useful building blocks and adrug analogue.

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Iridium‐Catalyzed Asymmetric Allylic Aromatization Reaction

Liu

Zheng

Yang

et al. 2019

Angewandte Chemie

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Sequence‐Dependent Stereodivergent Allylic Alkylation/Fluorination of Acyclic Ketones

et al. 2019

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The stereodivergent iridium-catalyzed allylic alkylation and fluorination of acyclic ketones is described. a-Pyridyl-a-fluoroketones with vicinal tertiary and quaternary stereocenters were obtained in moderate to excellent yields and stereoselectivities.D istinct from knowns tereodivergent synthesis,f or whicht wo different chiral catalysts are required in general, herein we report as equence-dependent stereodivergent synthesis.W itho nly as ingle chiral Ir catalyst, all four possible stereoisomers of the products were prepared from the same starting materials by simply adjusting the sequence of asymmetric allylic alkylation and fluorination and varying the absolute configuration of the Ir catalyst.

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Zirconium‐Catalyzed Atom‐Economical Synthesis of 1,1‐Diborylalkanes from Terminal and Internal Alkenes

Wang

Cui

et al. 2020

Angewandte Chemie

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A general and atom‐economical synthesis of 1,1‐diborylalkanes from alkenes and a borane without the need for an additional H2 acceptor is reported for the first time. The key to our success is the use of an earth‐abundant zirconium‐based catalyst, which allows a balance of self‐contradictory reactivities (dehydrogenative boration and hydroboration) to be achieved. Our method avoids using an excess amount of another alkene as an H2 acceptor, which was required in other reported systems. Furthermore, substrates such as simple long‐chain aliphatic alkenes that did not react before also underwent 1,1‐diboration in our system. Significantly, the unprecedented 1,1‐diboration of internal alkenes enabled the preparation of 1,1‐diborylalkanes.

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Generation and Application of (Diborylmethyl)zinc(II) Species: Access to Enantioenriched gem‐Diborylalkanes by an Asymmetric Allylic Substitution

Cited by 20 publications

References 126 publications

Iridium‐Catalyzed Asymmetric Allylic Aromatization Reaction

Iridium‐Catalyzed Asymmetric Allylic Aromatization Reaction

Sequence‐Dependent Stereodivergent Allylic Alkylation/Fluorination of Acyclic Ketones

Zirconium‐Catalyzed Atom‐Economical Synthesis of 1,1‐Diborylalkanes from Terminal and Internal Alkenes

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