A convenient, economical and scalable multi-gram synthesis of 1-vinylcyclopropyl 4-methylbenzenesulfonate

[3+2+2] Cycloaddition reactions are of key importance in organic chemistry for the synthesis of seven‐membered mono‐ and condensed carbocycles. This review article summarises the different reports on transition‐metal‐catalysed [3+2+2] cycloaddition reactions since 2000. Different transition‐metals, such as Ni, Rh, Pd, Co, or Ru, which have been earlier reported for higher order [3+2+2] cycloaddition reactions are summarized in this article. The [3+2+2] cycloadditions of different functionalized substrates afford cycloheptane derivatives, 6–7,5–7 condensed bicyclic carbocycles, or 5–7–5 or 6–7–5 condensed tricyclic carbocycles. These higher order cycloaddition reactions may provide an easy route for the total synthesis of natural products, or as a preferable key synthetic step leading to final structure.

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“…The enamine 71e and silyl enol ether 71f are formed by [3+2+2] cycloadditions of 69 with allenes 70e and 70f respectively. (Scheme ) , …”

Section: Rhodium‐catalyzed [3+2+2] Cycloaddition Reactionsmentioning

confidence: 99%

“…(Scheme 25). [44,45] Scheme 25. [(3+2)+2] carbocyclization of 69 with functionalized substituted allenes 70.…”

Section: Reactions Of Alkenylidenecyclopropanes and Alkynesmentioning

confidence: 99%

Transition‐Metal‐Catalyzed [3+2+2] Cycloaddition Reactions

et al. 2017

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“…To further improve the efficiency of this second-generation synthesis, we replaced the previous route to the 1-yne-vinylcyclopropane substrate of the [3 + 2 + 1] reaction, by using the allylboration reaction (Scheme 2). 12 Accordingly, we started our second-generation synthesis of clovan-2,9-dione (Scheme 3) from the common building block 2 13 and the known compound 3. 14 The allylboration of aldehyde 3 using allylboronate III generated in situ under Pdcatalyzed conditions gave alcohol (±)-4 in 62% yield.…”

mentioning

confidence: 99%

Total Synthesis of Clovan-2,9-dione via [3 + 2 + 1] Cycloaddition and Hydroformylation/Aldol Reaction

Zhou

Qin

et al. 2022

Org. Lett.

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Here we report the total synthesis of clovan-2,9-dione via Rhcatalyzed [3 + 2 + 1] cycloaddition/hydroformylation/aldol reaction. The [3 + 2 + 1] reaction of 1-yne-vinylcyclopropane and CO was used for the generation of a 5/6 bicyclic skeleton with a bridgehead vinyl group. The hydroformylation reaction converted the congested olefin of the [3 + 2 + 1] cycloadduct to a one-carbon elongated aldehyde, which underwent in situ aldol reaction, with the carbonyl group in the [3 + 2 + 1] cycloadduct, to generate the tricyclic bridged-ring skeleton of the target molecule.

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“…Additionally,t his process provides arare example of ahighly selective distal carbometalation of am ono-or 1,1-disubstituted allene in am etalcatalyzed cycloaddition reaction. Table 1o utlines the optimization and preliminary substrate scope for the rhodium-catalyzed [(3+ +2)+ +2] carbocyclization reaction with substituted allenes.T reatment of the ACP 1a [14] with the activated allene 2 (R 1 = CO 2 Et, R 2 = H) using [{Rh(cod)Cl} 2 ], modified with triphenylphosphite in pxylene at 100 8 8C, furnished the bicycloheptatriene 3a as the exclusive constitutional and stereoisomer in 62 %y ield favoring the E-configuration (entry 1). [15][16][17] Interestingly,t he analogous process with cationic complexes also provided 3a as the major adduct, albeit in significantly lower yield (entries 2a nd 3).…”

mentioning

confidence: 99%

Rhodium‐Catalyzed [(3+2)+2] Carbocyclization of Alkynylidenecyclopropanes with Substituted Allenes: Stereoselective Construction of Tri‐ and Tetrasubstituted Exocyclic Olefins

2015

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The development of the stereoselective rhodium-catalyzed [(3+2)+2] carbocyclization of alkynylidenecyclopropanes (ACPs) with substituted allenes is described. This work demonstrates that activated and unactivated allenes preferentially undergo carbometalation at the distal terminus to generate tri- and tetrasubstituted exocyclic olefins with a neutral rhodium catalyst. In addition, this method provides a strategy for the total synthesis of the guaiane family of sesquiterpenes, which are not directly accessible using alkynes as exogenous π-components. Finally, the preparation of the bicyclo[5.4.0]undecane ring system using a homologated ACP tether serves to further illustrate the versatility of this approach.

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A convenient, economical and scalable multi-gram synthesis of 1-vinylcyclopropyl 4-methylbenzenesulfonate

Abstract: The efficient and scalable synthesis of a valuable vinylcyclopropane (VCP) building block, which circumvents several problems encountered in previous syntheses, has been developed.

Cited by 4 publications

References 24 publications

Transition‐Metal‐Catalyzed [3+2+2] Cycloaddition Reactions

Transition‐Metal‐Catalyzed [3+2+2] Cycloaddition Reactions

Total Synthesis of Clovan-2,9-dione via [3 + 2 + 1] Cycloaddition and Hydroformylation/Aldol Reaction

Rhodium‐Catalyzed [(3+2)+2] Carbocyclization of Alkynylidenecyclopropanes with Substituted Allenes: Stereoselective Construction of Tri‐ and Tetrasubstituted Exocyclic Olefins

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