Luisa Carrillo’s research while affiliated with University of the Basque Country and other places

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Publications (165)


Figure 2. Organocatalytic activation manifolds typically employed for the activation of cyclopropanes in enantioselective ring-opening reactions.
Scheme 1. Pioneering examples on the use of organocatalysis for the activation of cyclopropanes.
Scheme 2. Iminium activation of cyclopropanecarbaldehydes in the reaction of omercabtobenzaldehydes.
Scheme 3. Chloride addition-induced ring-opening of meso-cyclopropanecarbaldehydes under iminium ion activation.
Scheme 8. Enamine activation in the enantioselective vinylcyclopropane/cyclopentene rearrangement.

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Organocatalysis as Enabling Tool for Enantioselective Ring-Opening Reactions of Cyclopropanes
  • Literature Review
  • Full-text available

June 2024

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66 Reads

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3 Citations

Chemical Communications

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Jose L. Vicario

The rich reactivity profile of cyclopropanes has been extensively explored to trigger new organic transformations that enable unusual disconnective approaches to synthesize molecular motifs that are not easily reached through...

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The Cloke–Wilson Rearrangement

March 2024

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28 Reads

The Cloke–Wilson rearrangement is a reaction that converts cyclopropanes bearing a carbonyl, thiocarbonyl, or imino group into dihydrofurans, dihydrothiophenes, or dihydropyrroles, respectively, in a transformation that is generally driven by the release of ring strain leading to the formation of significantly less‐strained five‐membered heterocyclic compounds. Although the Cloke–Wilson rearrangement has typically been carried out through thermal activation of the substrate (and very often requires harsh reaction conditions), more recent research has shown that this reaction can also be carried out using Brønsted acids, Lewis acids, Lewis bases, or organometallic complexes as catalysts or promoters. These advances have contributed to broadening the functional‐group tolerance of this transformation, and have allowed the Cloke–Wilson rearrangement to be used in the synthesis of densely functionalized heterocyclic scaffolds. This chapter covers all the examples reported in the literature in which a Cloke–Wilson rearrangement has been observed, including the standard reaction that involves formyl‐ or acyl‐substituted cyclopropanes that lead to dihydrofurans, and the heteroatom variants such as the aza‐ and sulfa‐Cloke–Wilson rearrangements. In addition, a detailed mechanistic explanation of the different general modes of substrate activation operating with each type of catalyst/promoter has also been included, together with representative examples of practical experimental protocols and some reports in which this reaction has been applied to total synthesis.





Asymmetric Dual Enamine Catalysis/Hydrogen Bonding Activation

July 2023

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116 Reads

Catalysts

Asymmetric enamine base activation of carbonyl compounds is a well-known and widely used strategy for providing functionalization of organic compounds in an efficient way. The use of solely organic substances, which in most cases are commercially available primary or secondary amines that are easy to obtain, avoids the use of hazardous substances or metal traces, making this type of catalysis a highly convenient methodology from a sustainable point of view. In many cases, the reactivity or the stereoselectivity obtained is far from being a practical and advantageous strategy; this can be improved by using a hydrogen bonding co-catalyst that can help during the activation of one species or by using a bifunctional catalyst that can direct the approximation of reagents during the reaction outcome. In this review, we describe the most efficient methodologies that make use of a dual activation of reagents for performing α-functionalization (enamine activation) or remote functionalization (such as dienamine or trienamine activation) of carbonyl compounds.


Desymmetrization of oxa(aza)norbornadienes through asymmetric catalysis.
Influence of the hydrazine N‐substituent on the reaction.
Scope of the reaction: Influence of the substituent at the azomethine carbon of the hydrazone reagents.
Scope of the reaction: oxa(aza)benzonorbornadiene component.
Proposed reaction mechanism for the formation of cycloaddition adducts.
Desymmetrization of Oxabenzonorbornadienes through Brønsted Acid‐Catalyzed Enantioselective (3+2) Cycloaddition with Hydrazones

June 2023

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26 Reads

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3 Citations

This work presents the desymmetrization of oxabenzonorbornadienes through the (3+2) cycloaddition reaction with hydrazones using a chiral Brønsted acid such as a BINOL‐derived phosphoramide. This chiral acid catalyst appears as the most effective mediator for the activation of the hydrazone via hydrazonium cation that reacts in a (3+2) fashion with the oxabenzonorbornadiene as the olefinic counterpart. Under the optimized conditions, the reaction provided selectively exo cycloaddition products in satisfactory yields and moderate stereoselectivities. The scope of the reaction was explored displaying 21 examples of these highly functionalized tetrahydroepoxybenzoindazole compounds. A reaction mechanism is proposed to explain the outcome of the reaction.


Organocatalytic Enantioselective Vinylcyclopropane‐Cyclopentene (VCP‐CP) Rearrangement

April 2023

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58 Reads

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11 Citations

We have demonstrated that the catalytic and enantioselective vinylcyclopropane‐cyclopentene rearrangement can be carried out on (vinylcyclopropyl)acetaldehydes through activation via enamine intermediates. The reaction makes use of racemic starting materials that, upon ring opening facilitated by the catalytic generation of a donor‐acceptor cyclopropane, deliver an acyclic iminium ion/dienolate intermediate in which all stereochemical information has been deleted. The final cyclization step forms the rearrangement product, showing that chirality transfer from the catalyst to the final compound is highly effective and leads to the stereocontrolled formation of a variety of structurally different cyclopentenes.


Brønsted Acid versus Phase‐Transfer Catalysis in the Enantioselective Transannular Aminohalogenation of Enesultams

October 2022

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141 Reads

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5 Citations

We have studied the enantioselective transannular aminohalogenation reaction of unsaturated medium‐sized cyclic benzosulfonamides by using both chiral Brønsted acid and phase‐transfer catalysis. Under optimized conditions, a variety of bicyclic adducts can be obtained with good yields and high enantioselectivities. The mechanism of the reaction was also studied by using computational tools; we observed that the reaction involves the participation of a conformer of the nine‐membered cyclic substrate with planar chirality in which the stereochemical outcome is controlled by the relative reactivity of the two pseudorotational enantiomers when interacting with the chiral catalyst.


Brønsted Acid versus Phase‐Transfer Catalysis in the Enantioselective Transannular Aminohalogenation of Enesultams

October 2022

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25 Reads

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1 Citation

Chemistry - A European Journal

Alice points out the preference of one conformational enantiomer by “crossing the mirror” thanks to the catalyst formed from the phosphoric acid and bromine “delivered” by N‐bromosuccinimide (NBS). Both the selected conformer and the new catalyst formed in situ merge their respective roads to converge on the product. More information can be found in the Research Article by U. Uria, P. Merino, J. L. Vicario, and co‐workers (DOI: 10.1002/chem.202202267).


Citations (56)


... Axially chiral biaryl compounds, such as 1,1'-bi-2-naphthol (BINOL) (figure 10(a)), 2,2'-bis(diphenylphosphino) -1,1'-binaphthyl (BINAP) ( figure 10(b)), and their derivatives are one of the most studied axially chiral molecules. They were widely used as catalysts [113][114][115] and also starting materials [116][117][118] in asymmetric synthesis. In axially chiral molecules, the hindered rotation around the chiral axis forms non-superimposable mirror images, which can be identified if the rotation has a minimum barrier of 23 kcal mol −1 . ...

Reference:

Synthesis and growth of solution-processed chiral perovskites
Desymmetrization of Oxabenzonorbornadienes through Brønsted Acid‐Catalyzed Enantioselective (3+2) Cycloaddition with Hydrazones

... It is of remark that 2-phenyl butanal reacted with methyl vinyl ketone, providing the corresponding adduct in excellent 91% ee enantioselectivity, albeit only 39% conversion was achieved after 20 h. Conjugate additions of aldehydes to Michael acceptors are a major C-C bond-forming reaction category within this area of catalysis [65][66][67][68][69][70][71]. Following up previous contributions in the area by the group, in 2015, Yoshida laboratory reported the addition of α-branched aldehydes to vinyl ketones 31 in the presence of 20 mol% of a chiral α-amino acid (e.g., phenylalanine C20) with the assistance of an accompanying base (Scheme 16) [72]. ...

Organocatalytic Enantioselective Conjugate Addition Reactions
  • Citing Book
  • October 2010

... In alternative, also Co-complex Λ-(S,S)-169 was highly effective for iodoamidation of unsaturated hydrazones 226 carried out with DIDMH, and the corresponding 5-iodomethyl 4,5dihydro-1H-pyrazoles 227 displaying at the tertiary center the same configuration as the bromomethyl derivatives 224, were isolated in good yield and high stereoselectivity (Scheme 65) [155]. It is worth noting that some dihydropyrazoles containing a quaternary chiral center were established as potent kinesin spindle protein (KSP) inhibitors, halting the cellular mitosis [156][157]. Thus, many efforts were directed towards asymmetric iodoamidation of unsaturated arenesulfonyl hydrazones directed towards preparation of dihydropyrazoles bearing either a quaternary center and a iodomethyl functionality suitable for further transformations. ...

Brønsted Acid versus Phase‐Transfer Catalysis in the Enantioselective Transannular Aminohalogenation of Enesultams

... The renewed interest in the Prins reaction stems from its ability to generate multifunctionalized carbohydrate scaffolds with diverse applications. A typical (Scheme 1) reaction pathway [31,32] involves the interaction of homoallylic alcohols 4 and carbonyl compounds in the presence of an acid catalyst, leading to the formation of an oxocarbenium ion intermediate 5. This intermediate undergoes π-cation cyclization, resulting in the formation of a tetrahydropyran intermediate 5a; then, through a nucleophilic attack, either the reaction proceeds intramolecularly or intermolecularly, which subsequently produces a highly functionalized and more complex molecular architecture 6. ...

Recent Advances in the Prins Reaction

ACS Omega

... Transannular cycloaddition reactions (TCRs) are useful for the synthesis of complex natural products and other biologically active compounds with high efficiency and stereoselectivity [1][2][3][4]. There are several different ways in which TCRs can occur, depending on the nature of the starting materials and the conditions used [5]. Some common types of TCRs include Diels-Alder reactions [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20], photocycloadditions [21][22][23][24][25][26][27][28], and other types of multistep cycloadditions [29]. ...

Recent Developments in Transannular Reactions
  • Citing Article
  • May 2022

Synthesis

... Enzymatic transformations are appreciated by many good features such as high selectivity, milder reaction conditions, and biocompatibility, which become an alternative powerful tool in organic synthesis. Therefore, the kinetic resolution (racemate resolution) with the use of enzymes, which relies on carrying out a stereoselective biotransformation, is one of the most frequently used methods due to the fact that, compared to the use of a "chiral pool", it is significantly less expensive and does not require the use of toxic and environmentally hazardous chemical compounds [6][7][8][9][10][11][12][13][14][15][16][17]. ...

Kinetic Resolution in Transannular Morita-Baylis-Hillman Reaction: An Approximation to the Synthesis of Sesquiterpenes from Guaiane Family

Catalysts

... The synthesis route is based on two stages: the first stage involves the synthesis of an advanced intermediate (cis-cycloadduct pyrrolidine) selectively, as a result of 1,3-dipolar cycloaddition between azomethine ylides (imine) and acrolein, using D-proline as a catalyst. This reaction can lead to two diastereoisomeric products, A (cis) and B (trans) [12], as shown in Fig. 2. In the second stage, several types of reactions are applied to the ciscycloadduct pyrrolidine, including oxidation, hydrolysis, and amide formation, to obtain the hepatitis C virus inhibitor (product C) as the target compound [12] (Fig. 2). In the present study, we propose cis-cycloadduct pyrrolidine (product A) as a candidate for HCV inhibition. ...

An Approach to the Synthesis of a Hepatitis C Virus Inhibitor through a Proline-Catalyzed 1,3-Dipolar Cycloaddition Using Acrolein
  • Citing Article
  • December 2021

Synthesis

... 10 Given the fame of these molecules, and their importance to medicine, it is remarkable that stereoselective methods using achiral starting materials are limited. 3 Current methods largely use one of two approaches: (1) desymmetrization of meso tropinone and its derivatives with stoichiometric chiral lithium amide bases, 11−14 and (2) enantioselective synthesis of the tropane scaffold where the stereochemical information is introduced concomitant with the formation of the bicycle. 15 Chiral auxiliary 16−20 and asymmetric catalytic approaches are known for the latter. ...

Enantioselective construction of the 8-azabicyclo[3.2.1]octane scaffold. Application to the synthesis of Tropane alkaloids
  • Citing Article
  • May 2021

Organic & Biomolecular Chemistry

... With a method to obtain all ΔE d contributions and ΔE i , we calculated the reaction profiles for the Diels-Alder reaction that yields the structures shown in Fig. 3. Entries 1-8 vary in the strength of the EWG, entry 9 extends the π system of the dienophile to study the effect of the EWG at long distances, entries 10-11 increase the size of the connector to yield larger cycles, and entry 12 is a transannular reaction, a special type of intramolecular reactions in which the reaction centers are present at opposite places of a macrocycle, and the process leads to the formation of polycyclic scaffolds in a single step [37][38][39]. Entries 9-12 contain an aldehyde group as EWG as the best compromise between relative strength and size (in terms of number of atoms and electrons), offering a consistent electron-withdrawing effect with little computational effort. Thus, their results should be compared with entry 5 only. ...

Catalytic enantioselective domino Michael/transannular aldol reaction under bifunctional catalysis

Chemical Communications

... The preparation of tropsulfimines 1 [24], vinylidenecyclopropane-diester 2 [25], and tropones 4 [26] and products 3 and 5 [19] followed the previous literature procedure. Compound 6a was detected by HRMS-ESI, and compound 6b was detected by MALDI. ...

γ-Substituted Allenic Amides in the Phosphine-Catalyzed Enantioselective Higher Order Cycloaddition with Azaheptafulvenes
  • Citing Article
  • May 2020

Organic Letters