Access to Highly Functionalized Cyclopentenones via Diastereoselective Pauson–Khand Reaction of Siloxy-Tethered 1,7-Enynes

Gallagher, Austin G.; Tian, Huan; Torres-Herrera, Osmar A.; Yin, Shuai; Xie, Anxin; Lange, Daniel M.; Wilson, Jerica K.; Mueller, Louis G.; Gau, Michael R.; Carroll, Patrick J.; Martinez‐Solorio, Dionicio

doi:10.1021/acs.orglett.9b03255

Cited by 16 publications

(6 citation statements)

References 75 publications

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“…Martínez-Solorio and co-workers reported an intramolecular PKR of Si−O tethered 1,7-enynes 35, affording cyclopentaoxasilinones 36 with high diastereoselectivity [56]. In contrast to previous silicon-based tethers, which reacted in low yields and resulted in unexpected byproducts, this transformation could be performed on a multigram scale and showed a wide substrate scope and functional group compatibility, as well as high diastereoselectivity [57,58].…”

Section: Scheme 11mentioning

confidence: 99%

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Pauson–Khand reaction of fluorinated compounds

Escorihuela¹,

Sedgwick²,

Llobat³

et al. 2020

Beilstein J. Org. Chem.

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The Pauson–Khand reaction (PKR) is one of the key methods for the construction of cyclopentenone derivatives, which can in turn undergo diverse chemical transformations to yield more complex biologically active molecules. Despite the increasing availability of fluorinated building blocks and methodologies to incorporate fluorine in compounds with biological interest, there have been few significant advances focused on the fluoro-Pauson–Khand reaction, both in the inter- and intramolecular versions. Furthermore, the use of vinyl fluorides as olefinic counterparts had been completely overlooked. In this review, we collect the advances both on the stoichiometric and catalytic intermolecular and intramolecular fluoro-Pauson–Khand reaction, with special attention to the PKR of enynes containing a fluoride moiety.

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Section: Scheme 11mentioning

confidence: 99%

“…Intramolecular PKR reported by the group of Martinez-Solorio[56]. Synthesis of fluorinated enynes 37[59].…”

mentioning

confidence: 99%

Pauson–Khand reaction of fluorinated compounds

Escorihuela¹,

Sedgwick²,

Llobat³

et al. 2020

Beilstein J. Org. Chem.

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“…By contrast, the intermolecular PKR enables chemists to envision a simple one-step synthesis of the cyclopentenones, yet the feasibility is traditionally limited (Scheme a, left). , Specific challenges are (1) alkenes show low reactivity; (2) unreliable control of regioselectivity with respect to the alkene component, and (3) the requirement of excess hazardous chemicals (e.g., pressurized CO gas or stoichiometric cobalt–carbonyl complexes). While several creative solutions have been demonstrated to overcome specific challenges, such as the alkene scope being improved by the preinstallation of a cleavable directing group , and the use of CO surrogates and less toxic metal catalysts/reagents, , these developments have not yet provided a general solution. Instead, approaches that are mechanistically distinct from the PKR introduce paradigms that are often complementary in nature.…”

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confidence: 99%

Modular Cyclopentenone Synthesis through the Catalytic Molecular Shuffling of Unsaturated Acid Chlorides and Alkynes

2020

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We describe a general strategy for the intermolecular synthesis of polysubstituted cyclopentenones using palladium catalysis. Overall, this reaction is achieved via a molecular shuffling process involving an alkyne, an α,β-unsaturated acid chloride, which serves as both the alkene and carbon monoxide source, and a hydrosilane to create three new C–C bonds. This new carbon monoxide-free pathway delivers the products with excellent yields. Furthermore, the regioselectivity is complementary to conventional methods for cyclopentenone synthesis. In addition, a set of regio- and chemodivergent reactions are presented to emphasize the synthetic potential of this novel strategy.

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“…The use of NMO as a reaction promoter has allowed the performance of PKR under remarkably mild conditions. Other alternative amine N ‐oxides trimethylamine N ‐oxide, TMANO), sulfides (butyl methyl sulfide, n ‐BuSMe) [76] and sulfoxides (dimethyl sulfoxide, DMSO) and cyclohexylamine [77] have been found to accelerate PKRs leading to excellent yields. Other ways of labializing CO ligands are based on the use of ultraviolet light and ultrasound irradiation, which have allowed elevated reaction efficiencies in reduced reaction times [78,79] …”

Section: Cycloaddition Reactionsmentioning

confidence: 99%

Fluorinated Imines in Tandem and Cycloaddition Reactions

Escorihuela

Fustero

2023

The Chemical Record

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The chemistry of fluorinated compounds has experienced extraordinary growth in recent decades due to the many and varied properties which many of the compounds that contain fluorinated groups possess. Among all of them, fluorinated chiral imines, in particular the Ellman's imines, are of great importance since they are some of the most interesting building blocks for the synthesis of a large number of enantioenriched carbocycles and heterocycles with extraordinary biological and synthetic properties. This personal account covers the most significant results obtained in our research group in the last two decades concerning asymmetric tandem reactions, paying special attention to the intramolecular aza‐Michael reaction (IMAMR), diversity oriented synthesis (DOS), asymmetric tandem reactions involving a p‐tolylsulfinyl group as chiral inducer and cycloaddition processes, in particular, the Pauson‐Khand reaction, [2+2+2]‐cycloadditions and metathesis reactions, starting mainly from enyne compounds and through the use of fluorinated chiral N‐sulfinyl imines and their derivatives as starting materials.

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Access to Highly Functionalized Cyclopentenones via Diastereoselective Pauson–Khand Reaction of Siloxy-Tethered 1,7-Enynes

Cited by 16 publications

References 75 publications

Pauson–Khand reaction of fluorinated compounds

Pauson–Khand reaction of fluorinated compounds

Modular Cyclopentenone Synthesis through the Catalytic Molecular Shuffling of Unsaturated Acid Chlorides and Alkynes

Fluorinated Imines in Tandem and Cycloaddition Reactions

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