Switch in Selectivity for Formal Hydroalkylation of 1,3‐Dienes and Enynes with Simple Hydrazones

Lv, Leiyang; Lin, Ying‐Chu; Qiu, Zihang; Li, Chao‐Jun

doi:10.1002/ange.201915875

Cited by 15 publications

(3 citation statements)

References 71 publications

(39 reference statements)

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“…Deuterium labelling studies were conducted using the heteroaryl ketone D-1 (79% deuterium content) as a substrate under the optimised conditions, with a significant level of the deuterated product D-2 (76% deuterium content) detected, suggesting that there were no reversible hydro-metallation in this process (Fig. 4c) 67,68 . Finally, we synthesised an aryl Pd complex (58-[Pd]), with 12 produced instead of 59 in the presence of 58-[Pd], benzyl bromide, and 1 (Fig.…”

Section: Resultsmentioning

confidence: 99%

Rapid syntheses of N-fused heterocycles via acyl-transfer in heteroaryl ketones

et al. 2022

Nat Commun

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The wide-ranging potencies of bioactive N-fused heterocycles inspire the development of synthetic transformations that simplify preparation of their complex, diverse structural motifs. Heteroaryl ketones are ubiquitous, readily available, and inexpensive molecular scaffolds, and are thus synthetically appealing as precursors in preparing N-fused heterocycles via intramolecular acyl-transfer. To best of our knowledge, acyl-transfer of unstrained heteroaryl ketones remains to be demonstrated. Here, we show an acyl transfer-annulation to convert heteroaryl ketones to N-fused heterocycles. Driven via aromatisation, the acyl of a heteroaryl ketone can be transferred from the carbon to the nitrogen of the corresponding heterocycle. The reaction commences with the spiroannulation of a heteroaryl ketone and an alkyl bromide, with the resulting spirocyclic intermediate undergoing aromatisation-driven intramolecular acyl transfer. The reaction conditions are optimised, with the reaction exhibiting a broad substrate scope in terms of the ketone and alkyl bromide. The utility of this protocol is further demonstrated via application to complex natural products and drug derivatives to yield heavily functionalised N-fused heterocycles.

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Section: Resultsmentioning

confidence: 99%

Rapid syntheses of N-fused heterocycles via acyl-transfer in heteroaryl ketones

et al. 2022

Nat Commun

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“…In summary, we have demonstrated a Ni-catalyzed fully intermolecuar regio-and stereo-selective cross-dialkylation of alkynes in the presence of alkyl halides and α,β-unsaturated compounds, affording stereodefined tri-and tetrasubstituted alkenes with multiple alkyl substitutions [58][59][60][61][62] . Notably, the reaction enables syn-selective dialkylation of alkynes with exclusive regioselectivity in the absence of any direction group, providing an alternative to access multi-substituted unfunctionalized alkenes from readilyaccessible reagents.…”

Section: Discussionmentioning

confidence: 96%

Ni-catalyzed regio- and stereo-defined intermolecular cross-electrophile dialkylation of alkynes without directing group

2021

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The development of straightforward synthesis of regio- and stereodefined alkenes with multiple aliphatic substituents under mild conditions is an unmet challenge owing to competitive β-hydride elimination and selectivity issues. Herein, we report the nickel-catalyzed intermolecular cross-dialkylation of alkynes devoid of directing or activating groups to afford multiple aliphatic substituted alkenes in a syn-selective fashion at room temperature. The combination of two-electron oxidative cyclometallation and single-electron cross-electrophile coupling of nickel enables the syn-cross-dialkylation of alkynes at room temperature. This reductive protocol enables the sequential installation of two different alkyl substituents onto alkynes in a regio- and stereo-selective manner, circumventing the tedious preformation of sensitive organometallic reagents. The synthetic utility of this protocol is demonstrated by efficient synthesis of multi-substituted unfunctionalized alkenes and diverse transformations of the product.

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“…The recent increase in the exploration of new types of nucleophiles further extends the synthetic utility of this reaction (11)(12)(13)(14). Recently, we have developed the umpolung carbonyls as novel nucleophiles to couple with alkynes (15), 1,3-dienes (16,17), allyl acetates (18), and functionalized cyclopropane derivatives (19,20) and afforded a series of functionalized alkenes. The mild reaction conditions and tolerance of various functional groups (even water) make this strategy a great opportunity for the direct functionalization of carbohydrates.…”

Section: Introductionmentioning

confidence: 99%

Umpolung carbonyls enable direct allylation and olefination of carbohydrates

et al. 2022

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Mother Nature has its own arts to build a vast number of carbohydrates; however, there is still a lack of tools for selective functionalization of native carbohydrates through C─C bond formation. Such a long-standing challenge for the synthetic community lies into the intrinsic problems related to the innate properties of carbohydrates, e.g., the ease to oligomerization or polymerization, the difficulty of chemoselectivity control in the presence of multiple hydroxyl groups, the great challenge to retain the multiple chiral centers during the transformation, etc. Here, by applying an umpolung strategy of carbohydrate carbonyls, we report a direct deoxygenative allylation and olefination of carbohydrates to tackle the abovementioned issues. The reaction is compatible with a wide range of natural carbohydrates, providing a direct synthetic method to use carbohydrates as multiple C-centered chiral synthons to achieve C─C bond cross-coupling reactions. Furthermore, the synthetic applicability is demonstrated by late-stage modifications of natural products and pharmaceutical derivatives.

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Switch in Selectivity for Formal Hydroalkylation of 1,3‐Dienes and Enynes with Simple Hydrazones

Cited by 15 publications

References 71 publications

Rapid syntheses of N-fused heterocycles via acyl-transfer in heteroaryl ketones

Rapid syntheses of N-fused heterocycles via acyl-transfer in heteroaryl ketones

Ni-catalyzed regio- and stereo-defined intermolecular cross-electrophile dialkylation of alkynes without directing group

Umpolung carbonyls enable direct allylation and olefination of carbohydrates

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