Tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds

Miró, Javier; Sánchez‐Roselló, María; Sanz, Álvaro; Rabasa, Fernando; Pozo, Carlos del; Fustero, Santos

doi:10.3762/bjoc.11.161

Cited by 8 publications

(3 citation statements)

References 32 publications

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“…A second parameter to consider is the effect of the presence of additives. Indeed, it has been demonstrated that the addition of several molecules during the metathesis reaction (such as acetic acid, benzoquinones, or thioureas) [22][23][24] positively affect the final catalytic properties of the organometallic compound. Different additives could result in completely different active species from the same Grubbs catalyst and trigger different catalytic pathways to produce structurally unique products.…”

Section: Activity Of Soluble Hoveyda-grubbs Second-generation Catalysmentioning

confidence: 99%

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

2016

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Heterogeneous catalysts have been synthesized by the conjugation of Hoveyda-Grubbs second-generation catalyst with a lipase. The catalytic properties of the organometallic compound in solution were firstly optimized, evaluating the activity of Ru in the ring-closing metathesis of diethyldiallymalonate at 25 • C at different solvents and in the presence of different additives. The best result was found using tetrahydrofuran as a solvent. Some additives such as phenylboronic acid or polyetheneglycol slightly improved the activity of the Ru catalyst whereas others, such as pyridine or dipeptides affected it negatively. The organometallic compound immobilized on functionalized-surface materials activated with boronic acid or epoxy groups (around 50-60 µg per mg support) and showed 50% conversion at 24 h in the ring-closing metathesis. Cross-linked enzyme aggregates (CLEA's) of the Hoveyda-Grubbs second-generation catalyst with Candida antarctica lipase (CAL-B) were prepared, although low Ru catalyst was found to be translated in low conversion. Therefore, a sol-gel preparation of the Hoveyda-Grubbs second-generation and CAL-B was performed. This catalyst exhibited good activity in the metathesis of diethyldiallymalonate in toluene and in aqueous media. Finally, a new sustainable approach was used by the conjugation lipase-Grubbs in solid phase in aqueous media. Two strategies were used: one using lipase previously covalently immobilized on an epoxy-Sepharose support (hydrophilic matrix) and then conjugated with grubbs; and in the second, the free lipase was incubated with organometallic in aqueous solution and then immobilized on epoxy-Sepharose. The different catalysts showed excellent conversion values in the ring-closing metathesis of diethyldiallymalonate in aqueous media at 25 • C.

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Section: Activity Of Soluble Hoveyda-grubbs Second-generation Catalysmentioning

confidence: 99%

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

2016

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“…In 2015, Fustero’s group has reported a tandem CEM and intramolecular DA reaction methodology for the generation of linear bicyclic ketone, lactone, and lactam scaffolds in a simple manner with good diastereoselectivity (Scheme 30). 23 In this regard, various conjugated ketones, esters, and amides bearing an alkene moiety 113 were reacted with different aromatic alkynes 114 in the presence of HG-II catalyst to obtain the bicyclic ketone, lactones, and lactams 115 . The resulting bicyclic heterocycles 115 were formed via tandem CEM and an intramolecular DA reaction sequence.…”

Section: Introductionmentioning

confidence: 99%

Diversity-Oriented Approaches to Polycycles and Heterocycles via Enyne Metathesis and Diels–Alder Reaction as Key Steps

Kotha

Chavan²,

Goyal

2019

ACS Omega

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Enyne metathesis (EM) has extensively been used to prepare diverse polycycles and heterocycles. EM in combination with Diels–Alder (DA) reaction has been used to prepare densely functionalized targets in a simple manner. In this mini-review, we discuss the various diversity-oriented approaches reported from our laboratory to prepare a variety of organic frameworks by a synergistic combination of EM and DA reactions. Some of the end products are useful intermediates for the synthesis of complex organic targets.

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“…Synthèse de tris-fullérodendrimères de type Janus par une combinaison « métathèse croisée d'oléfinesaldolisation ».Nous aimerions également appliquer une réaction tandem métathèse croisée d'enyne/Diels-Alder décrite dans la litérature81,82 pour préparer des tris-fullérodendrimères comportant trois mésogènes différents (schéma 21). La synthèse débute par la réaction de métathèse croisée d'enyne entre une oléfine de type I et un alcyne terminal pour donner l'intermédaire diènique.Ce diène est par la suite mis en jeu dans la réaction de Diels-Alder avec un diénophile pour conduire au produit désiré.…”

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Synthèse et étude de [60]fullérodendrimères chiraux liquides-cristallins

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Fullerene-containing liquid crystals are interesting materials since they combine the properties of C60 (electrochemical and photophysical behavior) with the characteristics of liquid crystals (self-organization and order). In the first part, we prepared a family of bis-[60]fullerodendrimers and a series of tris-[60]fullerodendrimers containing chiral mesogens. The aim was to study the influence of C60 on the formation and structural organization of the chiral smectic C (SmC *) phase which can generate ferroelectric properties as well as to develop a synthetic strategy in order to increase the density of C60 in liquid-crystalline scaffolds. Our results demonstrate that it is possible to incorporate up to three isotropic C60 units within mesophases. In the second and third projects, we synthesized Janus bis- and tris-[60]fullerodendrimers. They are functionalized with two different chiral mesogens, one mesogen promoting lamellar organizations and one mesogen displaying the chiral nematic (N*) phase. Our objective was to study the influence of 1) each source of chirality, 2) the generation of each dendron and 3) the content of C60 on the mesomorphic properties. Our studies demonstrate that the liquid-crystalline properties can be modified and tuned by adjusting the size of dendritic frameworks. The Janus architecture of dendrimers increases the possibilities for controlling the mesomorphic properties with respect to conventional dendrimers. Finally, we developed a synthetic approach to insert three types of mesogens into tris-[60]fullerodendrimers. The final products, which bear two calamitic mesogens and one discotic mesogen, are accessible for the first time. The aim was to explore the influence of each mesogen on the formation of the mesophases and to obtain thermotropic liquid crystals based on C60 which can present, within the same sequence, lamellar, nematic and columnar mesophases.

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Tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds

Cited by 8 publications

References 32 publications

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

Diversity-Oriented Approaches to Polycycles and Heterocycles via Enyne Metathesis and Diels–Alder Reaction as Key Steps

Synthèse et étude de [60]fullérodendrimères chiraux liquides-cristallins

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