Catalytic Deallylation of Allyl‐ and Diallylmalonates.

Nečas, David; Turský, Matyáš; Kotora, Martin

doi:10.1002/chin.200449042

Cited by 3 publications

(4 citation statements)

References 5 publications

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“…The desired 2-aryl-1,3-cyclohexanedione could be obtained via deallylation. After the C2-arylation of 2-allyl-1,3-cyclohexanedione, the resulting arylation product 85 was subsequently applied in Kotora's nickel-catalyzed deallylation 76 to afford 2aryl-1,3-cyclohexanedione 86 (Scheme 48c).…”

Section: Addition/β-elimination Cascadementioning

confidence: 99%

Carbon–Carbon Bond Cleavage at Allylic Positions: Retro-allylation and Deallylation

Nogi

Yorimitsu

2020

Chem. Rev.

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The development of C−C bond-cleaving transformations is an issue in modern organic chemistry that is as challenging as it is important. Among these transformations, the retroallylation and deallylation of allylic compounds are uniquely intriguing methods for the cleavage of C−C σ bonds at the allylic position. Retro-allylation is regarded as a prospective method for the generation of highly valuable regio-and stereodefined allylic metal compounds. Because the C−C cleavage proceeds via a favorable six-membered chairlike transition state, the regio-and stereochemical information on the starting homoallylic alcohols can be transferred onto the products. Moreover, retro-allylation can also be achieved using enantioselective C−C cleavage powered by chiral catalysts for the synthesis of enantiomerically enriched compounds. As a result of these attractive features, retro-allylation has wide utility in regio-, stereo-, and enantioselective synthesis. Deallylation is C−C σ-bond cleavage involving the departure of an allylic fragment and the formation of a relatively stable carbanion or radical, and it proceeds via either oxidative addition to a low-valent metal or an addition/β-elimination cascade. The removal of the versatile allylic group might seem to be unproductive; however, this unique transformation offers the opportunity of using the allylic group as a protective group for acidic C−H bonds. This Review aims to exhibit the synthetic utility as well as the uniqueness of these two C−C σ-bond cleavage methods by presenting a wide range of transformations of allylic compounds with the aid of main group metals, transition-metal catalysts, and radical species.

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Section: Addition/β-elimination Cascadementioning

confidence: 99%

Carbon–Carbon Bond Cleavage at Allylic Positions: Retro-allylation and Deallylation

Nogi

Yorimitsu

2020

Chem. Rev.

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“…The analytical data were in good agreement with those reported in literature. 34 Procedure for the Preparation of Hydroborane 2b. 35 Hydroborane 2b was prepared using a procedure similar to the one for the preparation of borane 2c.…”

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confidence: 99%

Palladium-Catalyzed Hydroboration/Cyclization of 1,n-Dienes

2023

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While the hydroboration of alkenes is well established, the corresponding cyclization reaction of dienes remains challenging. Here, we report a new method for hydroboration/cyclization applicable to various 1,n-dienes and hydroboranes. The method features the direct synthesis of borylalkyl cyclopentanes from common 1,6-dienes, which is highlighted by syntheses of elaborated pyrrolidine cores from easily accessible diallylamines. Notably, 1,n-dienes (n > 6) also undergo five-membered ring formation, offering "remote" hydroboration/ cyclization that would be otherwise difficult to achieve.

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“…Thus, an efficient twostep sequence was developed in which Pd-catalyzed bisallylation 22 was followed by Ni-catalyzed mono-deallylation. 23 Finally, regioselective O-methylation (4:1 C3-OMe versus C5-OMe, > 20:1 after purification), cross-metathesis 24 with Scheme 5. Synthesis of (−)-Cajanusine Journal of the American Chemical Society isobutene, and deprotection allowed for synthesis of (−)-cajanusine (1).…”

mentioning

confidence: 99%

“…Thus, an efficient twostep sequence was developed in which Pd-catalyzed bisallylation 22 was followed by Ni-catalyzed mono-deallylation. 23 Finally, regioselective O-methylation (4:1 C3-OMe versus C5-OMe, > 20:1 after purification), cross-metathesis 24 isobutene, and deprotection allowed for synthesis of (−)-cajanusine (1). Due to the scalability and simplicity of many of the steps, >100 mg of cajanusine was easily prepared (98 mg was prepared in one reaction).…”

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confidence: 99%

Evolution of a Strategy for the Enantioselective Synthesis of (−)-Cajanusine

2020

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The first enantioselective synthesis of (−)-cajanusine is presented. Key features of the route include a rapid synthesis of the [4.2.0]bicyclooctane core by an enantioselective isomerization/stereoselective [2+2]-cycloaddition strategy as well as prominent use of catalytic methods for bond construction. The evolution of the approach is also presented that highlights unexpected roadblocks and how novel solutions were developed.

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Catalytic Deallylation of Allyl‐ and Diallylmalonates.

Cited by 3 publications

References 5 publications

Carbon–Carbon Bond Cleavage at Allylic Positions: Retro-allylation and Deallylation

Carbon–Carbon Bond Cleavage at Allylic Positions: Retro-allylation and Deallylation

Palladium-Catalyzed Hydroboration/Cyclization of 1,n-Dienes

Evolution of a Strategy for the Enantioselective Synthesis of (−)-Cajanusine

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