Role of the <i>g</i><i>em</i>-Difluoro Moiety in the Tandem Ring-Closing Metathesis−Olefin Isomerization:  Regioselective Preparation of Unsaturated Lactams

Fustero, Santos; Sánchez‐Roselló, María; Jiménez, Daniel; Sanz‐Cervera, Juan F.; Pozo, Carlos del; Aceña, José Luis

doi:10.1021/jo0525635

Cited by 89 publications

(54 citation statements)

References 34 publications

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“…[69] Fustero et al have reported the synthesis of various fluorinated nitrogen-containing six or seven-membered rings by way of RCM (Scheme 41). [70][71][72] Reactions performed from secondary amines 104 and 106 protected with a p-MeOC 6 H 4 (PMP) group afforded the expected cyclized products in low to good yields. Formation of unproductive six-membered metallacycle intermediates by chelation of ruthenium complexes and the ester carbonyl oxygen may partly explain the difference of reactivity between 104 and 106.…”

Section: Ruthenium-catalyzed Metathesis Of Phenylamines and Analoguesmentioning

confidence: 99%

Olefin Metathesis of Amine‐Containing Systems: Beyond the Current Consensus

Compain¹

2007

Adv Synth Catal

163

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Olefin metathesis is one of the most powerful synthetic tool to access amine-containing heterocycles and alkaloids. A major drawback associated with the use of amines concerns their ability to coordinate to metal-alkylidene complexes and to interfere unproductively with catalytic activity. Based on literature precedents, it has been established as a "dogma" that efficient metathesis reactions are suppressed in the presence of basic amines and that such substrates must invariably be deactivated by conversion of the amines to the corresponding carbamates or ammonium salts. However, an increasing number of examples of amine-containing compounds that are good substrates for metathesis is being reported in the literature. How can this "non-classical" reactivity be rationalized and exploited? The purpose of this review is to provide an overview of successful metathesis reactions performed with aminecontaining compounds in order to allow some guidelines to be formulated. A special emphasis is placed on the different parameters that may influence the outcome of the reaction such as steric effects, amine basicity, and the nature of the catalyst.

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Section: Ruthenium-catalyzed Metathesis Of Phenylamines and Analoguesmentioning

confidence: 99%

Olefin Metathesis of Amine‐Containing Systems: Beyond the Current Consensus

Compain¹

2007

Adv Synth Catal

163

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“…[15] It is most likely that C decomposes bimolecularly under the reaction conditions to a ruthenium hydride species, [54] which has previously been postulated as the actual isomerization catalyst. [55,56] The necessity for a certain degree of steric hindrance in the OH protecting group in order to obtain preparatively useful selectivities towards dihydrofurans 8 was strongly underlined when RCM of methyl ether 6e …”

Section: Regioselective Double Rcm: Fused Vs Dumbbelltype Bicyclic Smentioning

confidence: 99%

Synthesis of Dihydrofurans and Dihydropyrans with Unsaturated Side Chains Based on Ring Size‐Selective Ring‐Closing Metathesis

Schmidt

Nave

2007

Adv Synth Catal

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Enantiomerically pure 1,5-hexadiene-3,4-diol, derived from d-mannitol in a few steps, may serve as a starting material for enantiopure dihydropyrans and dihydrofurans bearing an unsaturated side chain which is amenable for further synthetic transformations. The synthesis relies on a ring sizeselective ring-closing metathesis reaction of a triene. Most likely, a catalyst-directing effect of an allylic hydroxy group is responsible for the selectivity.

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“…Next, we focused our attention on the amide [14] 6s bearing also a chloro-substituted C=C double bond (Table 4). Its corresponding RCM product, lactam 6p, is an important fragment for the construction of building blocks through cross-coupling reactions.…”

Section: Resultsmentioning

confidence: 99%

Microwave‐Assisted Ruthenium‐Catalysed Olefin Metathesis in Fluorinated Aromatic Hydrocarbons: A Beneficial Combination

et al. 2011

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International audienceHigh conversions in ruthenium-based olefin metathesis of demanding substrates are commonly forced by using a high loading of a catalyst and conducting reactions at elevated temperature for extended times. However, in many cases this approach is not fully effective. In this article we present that fluorinated aromatic hydrocarbons (FAH) combined with microwave (MW) irradiation using a commercially available ruthenium-based pre-catalyst creates attractive reaction conditions for promoting challenging olefin metathesis transformations

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Role of the gem-Difluoro Moiety in the Tandem Ring-Closing Metathesis−Olefin Isomerization: Regioselective Preparation of Unsaturated Lactams

Cited by 89 publications

References 34 publications

Olefin Metathesis of Amine‐Containing Systems: Beyond the Current Consensus

Olefin Metathesis of Amine‐Containing Systems: Beyond the Current Consensus

Synthesis of Dihydrofurans and Dihydropyrans with Unsaturated Side Chains Based on Ring Size‐Selective Ring‐Closing Metathesis

Microwave‐Assisted Ruthenium‐Catalysed Olefin Metathesis in Fluorinated Aromatic Hydrocarbons: A Beneficial Combination

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