Chemodivergent transformations of amides using gem-diborylalkanes as pro-nucleophiles

Sun, Wei; Wang, Lu; Hu, Yue; Wu, Xudong; Xia, Chungu; Liu, Chao

doi:10.1038/s41467-020-16948-5

Cited by 56 publications

(22 citation statements)

References 65 publications

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“…Initially, the reaction of an aldehyde with a diboron compound simultaneously forms the C–B and O–B bonds of Int I . As a pivotal step, the carbonyl bis-borylation not only gives the desired C–B bond but also reduces the CO bond order . Considering its similarity to alkene vicinal diboration, a highly electrophilic diboron reagent with a compatible basic activator would be beneficial .…”

Section: Results and Discussionmentioning

confidence: 99%

Metal-Free Direct Deoxygenative Borylation of Aldehydes and Ketones

Wang

Qiu

et al. 2020

J. Am. Chem. Soc.

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Direct conversion of aldehydes and ketones into alkylboronic esters via deoxygenative borylation represents an unknown yet highly desirable transformation. Herein, we present a one-step and metal-free method for carbonyl deoxy-borylation under mild conditions. A wide range of aromatic aldehydes and ketones are tolerated and successfully converted into the corresponding benzylboronates. By the same deoxygenation manifold with aliphatic aldehydes and ketones, we also enable a concise synthesis of 1,1,2-tris(boronates), a family of compounds that currently lack efficient synthetic methods. Given its simplicity and versatility, we expect that this novel borylation approach could show great promise in organoboron synthesis and inspire more carbonyl deoxygenative transformations in both academic and industrial settings.

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Section: Results and Discussionmentioning

confidence: 99%

Metal-Free Direct Deoxygenative Borylation of Aldehydes and Ketones

Wang

Qiu

et al. 2020

J. Am. Chem. Soc.

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“…[10] Stable twisted amides have also been successfully employed by Szostak and co‐workers as effective acylating reagents to promote the chemoselective 1,2‐addition reaction of highly polarized s ‐block organometallic reagents by exploiting pyramidalization as a reactive controlling feature (Figure 1 b). [9c, 11] Reaction of Grignard reagents with N ‐Boc protected amides under kinetic control [8b] and the transformation of amides using gem ‐diborylalkanes as pro‐nucleophiles are other viable alternatives in using modified amides [9b] . A second approach includes the chemical activation of the amide functional group via highly electrophilic intermediates (Figure 1 c), [6a, 12] whereas a third synthetic route makes use of transition metal‐catalyzed C‐N activation reactions of activated amides delivering a metal acylating agent (Figure 1 d).…”

Section: Introductionmentioning

confidence: 99%

A Fast and General Route to Ketones from Amides and Organolithium Compounds under Aerobic Conditions: Synthetic and Mechanistic Aspects

Ghinato

Territo

Maranzana

et al. 2021

Chemistry A European J

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We report that the nucleophilic acyl substitution reaction of aliphatic and (hetero)aromatic amides by organolithium reagents proceeds quickly (20 s reaction time), efficiently, and chemoselectively with a broad substrate scope in the environmentally responsible cyclopentyl methyl ether, at ambient temperature and under air, to provide ketones in up to 93 % yield with an effective suppression of the notorious over‐addition reaction. Detailed DFT calculations and NMR investigations support the experimental results. The described methodology was proven to be amenable to scale‐up and recyclability protocols. Contrasting classical procedures carried out under inert atmospheres, this work lays the foundation for a profound paradigm shift of the reactivity of carboxylic acid amides with organolithiums, with ketones being straightforwardly obtained by simply combining the reagents under aerobic conditions and with no need of using previously modified or pre‐activated amides, as recommended.

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“…In 2020, Sun et al [126] . reported a novel synthesis of α ‐alkylated β ‐keto amides 263 by the reaction of N ‐Boc protected aryl amides 260 with gem ‐diborylalkanes 261 (Scheme 49).…”

Section: Synthesis Of β‐Keto Amidesmentioning

confidence: 99%

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

Zheng

et al. 2021

Eur J Org Chem

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β‐Keto amides are a versatile class of compounds that find wide applications in organic chemistry owing to the juxtaposition of multiple reaction sites within their molecular structures. Due to the importance of β‐keto amides in modern organic chemistry, numerous novel preparation methods, synthetic applications and unprecedented reactivities have been recorded over the past decade. Taking advantage of transition‐metal‐catalysis and organocatalysis, β‐keto amides have emerged into a jack‐of‐all‐trades building block for many stereoselective or tandemized multicomponent reactions. But so far, no reviews have been documented on these recent achievements with β‐keto amides. Our Review aims to provide a thorough summary regarding: (a) the synthesis of β‐keto amides, (b) the reactivities of β‐keto amides, (c) the synthetic applications of β‐keto amides in various important heterocyclic compounds, and (d) the coordination of β‐keto amides with main group elements and transition metals and the relevant applications.

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Chemodivergent transformations of amides using gem-diborylalkanes as pro-nucleophiles

Cited by 56 publications

References 65 publications

Metal-Free Direct Deoxygenative Borylation of Aldehydes and Ketones

Metal-Free Direct Deoxygenative Borylation of Aldehydes and Ketones

A Fast and General Route to Ketones from Amides and Organolithium Compounds under Aerobic Conditions: Synthetic and Mechanistic Aspects

β‐Keto Amides: A Jack‐of‐All‐Trades Building Block in Organic Chemistry

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