Synthesis of 1,1-diboronate esters by cobalt-catalyzed sequential hydroboration of terminal alkynes

Zuo, Ziqing; Huang, Zheng

doi:10.1039/c5qo00426h

Cited by 87 publications

(30 citation statements)

References 74 publications

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“…15 As the majority of new catalytic hydroboration systems contain nucleophilic motifs, it is necessary to exclude nucleophile-promoted BH3 formation from 'true' catalysis by the metal/metalloid species. The nucleophilic motifs can be separated into three classes: pre-catalyst activators, [15][16][17][18][19][20][21][22] sacrificial ligands [23][24][25] and inherent nucleophilic catalysts (Scheme 1C). [26][27][28][29][30][31] To distinguish between 'true' catalysis and BH3 catalysis for reactions using HBpin it was necessary to: 1.…”

Section: Hidden Boron Catalysis: Nucleophile-promoted Decomposition Of Hbpinmentioning

confidence: 99%

Hidden Boron Catalysis: Nucleophile-Promoted Decomposition of HBpin

2020

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Simple nucleophiles with structural similarities to known hydroboration catalysts can readily mediate the formation of BH 3 and borohydride species from pinacolborane (HBpin). Alkyne and alkene hydroboration reactions were successfully mediated by nucleophiles through BH 3 generation, with BH 3 -catalyzed hydroboration found to dominate catalysis. NMR spectroscopy and kinetic analyses showed that the nucleophiles NaO t Bu, Na[N(SiMe 3 ) 2 ], n Bu 2 Mg, and n BuLi only promoted the formation of BH 3 and were not "true" hydroboration catalysts.

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Section: Hidden Boron Catalysis: Nucleophile-promoted Decomposition Of Hbpinmentioning

confidence: 99%

Hidden Boron Catalysis: Nucleophile-Promoted Decomposition of HBpin

2020

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“…Interestingly, gem-bis(boryl)alkanes can generate two types of carboanions, monoboryl-or gem-bis(boryl)-functionalized carboanions, via deprotonation by LiTMP (lithium tetramethylpiperidide) or alkoxide-induced deborylation 11,12 . Over past decades, series of catalytic reactions have been developed to access these gem-bis(boryl) compounds [13][14][15][16][17] , such as double hydroboration of alkynes [18][19][20] , diborylation of alkenes 21,22 , hydroboration of 1-borylalkene [23][24][25] , or C-H borylation reactions [26][27][28][29] . Nevertheless, a general and practical approach that combines high catalytic activity, easy accessibility and handling of starting materials, and structural diversity of gem-bis(boryl) products is still lacking.…”

mentioning

confidence: 99%

Versatile cobalt-catalyzed regioselective chain-walking double hydroboration of 1,n-dienes to access gem-bis(boryl)alkanes

2020

Nat Commun

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Double hydroboration of dienes is the addition of a hydrogen and a boryl group to the two double bonds of a diene molecule and represents a straightforward and effective protocol to prepare synthetically versatile bis(boryl)alkanes, provided that this reaction occurs selectively. However, this reaction can potentially yield several isomeric organoboron products, and it still remains a challenge to control the regioselectivity of this reaction, which allows the selective production of a single organoboron product, in particular, for a broad scope of dienes. By employing a readily available cobalt catalyst, here we show that this double hydroboration yields synthetically useful gem-bis(boryl)alkanes with excellent regioselectivity. In addition, the scope of dienes for this reaction is broad and encompasses a wide range of conjugated and non-conjugated dienes. Furthermore, mechanistic studies indicate that this cobalt-catalyzed double hydroboration occurs through boryl-directed chain-walking hydroboration of alkenylboronates generated from anti-Markovnikov 1,2-hydroboration of 1,n-diene.

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“…Transition metal catalyzed synthesis of 1,1-diborylalkanes from terminal alkenes ( e ). Previous work was reported for preparation of 1,1-diborylalkanes from 1,1-dihalides 11 , 21 , 46 , terminal alkynes 47 – 49 , carbene insertion 50 , 51 , hydroboration of borylalkenes 42 , 43 or C-H activation 52 – 54 ( f ) …”

Section: Introductionmentioning

confidence: 99%

Nickel-catalyzed synthesis of 1,1-diborylalkanes from terminal alkenes

et al. 2017

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Organoboron compounds play an irreplaceable role in synthetic chemistry and the related transformations based on the unique reactivity of C–B bond are potentially the most efficient methods for the synthesis of organic molecules. The synthetic importance of multiboron compounds in C–C bond formation and function transformation reactions is growing and the related borations of activated or nonactivated alkenes have been developed recently. However, introducing directly two boron moieties into the terminal sites of alkenes giving 1,1-diborylalkanes in a catalytic fashion has not been explored yet. Here we describe a synthetic strategy of 1,1-diborylalkanes via a Ni-catalyzed 1,1-diboration of readily available terminal alkenes. This methodology shows high level of chemoselectivity and regioselectivity and can be used to convert a large variety of terminal alkenes, such as vinylarenes, aliphatic alkenes and lower alkenes, to 1,1-diborylalkanes.

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Synthesis of 1,1-diboronate esters by cobalt-catalyzed sequential hydroboration of terminal alkynes

Abstract: Co-catalyzed sequential hydroborations of alkyl and aryl alkynes with pinacolborane produce 1,1-diboronate esters with high selectivity and yields.

Cited by 87 publications

References 74 publications

Hidden Boron Catalysis: Nucleophile-Promoted Decomposition of HBpin

Hidden Boron Catalysis: Nucleophile-Promoted Decomposition of HBpin

Versatile cobalt-catalyzed regioselective chain-walking double hydroboration of 1,n-dienes to access gem-bis(boryl)alkanes

Nickel-catalyzed synthesis of 1,1-diborylalkanes from terminal alkenes

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