Enantioselective, transition metal catalyzed cycloisomerizations

Marinetti, Angéla; Jullien, Hélène; Voituriez, Arnaud

doi:10.1039/c2cs35020c

Cited by 234 publications

(67 citation statements)

References 167 publications

(193 reference statements)

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“…Similarly to its oxidation in dichloromethane, the oxidation of IPr·CuCl occurred in N,Ndimethylformamide (DMF) at around + 1.3 V/SCE (wave O 1 ; SCE = saturated calomel electrode). [31] Good yields of the bicyclic product 13 were observed with the complexes 7 a·AuCl and 7 b·AuCl in reactions featuring quite promising enantioselectivities (the product was formed with 43 and 59 % ee, respectively). The absence of electrochemical signals for 7 a·CuCl cannot be due to a slower diffusion rate than that of IPr·CuCl, since it was shown previously that a copper-capped salen-cyclodextrin complex, in which the metal was placed at the entrance of the cavity, could be reduced and oxidized electrochemically.…”

Section: Methodsmentioning

confidence: 96%

NHC‐Capped Cyclodextrins (ICyDs): Insulated Metal Complexes, Commutable Multicoordination Sphere, and Cavity‐Dependent Catalysis

Guitet¹,

Zhang²,

Marcelo³

et al. 2013

Angew Chem Int Ed

138

117

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Metal centers associated with cavities have attracted much attention, mainly because of their resemblance to metalloenzymes.[1] Among concave molecules with a cavity, cyclodextrins (CDs) are unique owing to their natural occurrence, their hydrosolubility, and the structure of their cavity. Unlike any other cavity, in particular those based on aromatic rings, their interior is carpeted with hydrogen atoms, which confer hydrophobicity and introduce additional van der Waals interactions. Therefore, CDs are widely used to host hydrophobic molecules in polar solvents. The possibility of converting cyclodextrins into enzyme mimics very soon attracted the interest of scientists.[2] More specifically, for CDs to be used to mimic metalloenzymes, a metal must be attached to the CD scaffold. [3] Owing to the size of the cavity, two different ways to append the metal can be considered for the study of two different phenomena. First, the metal can be positioned at the entrance of the cavity to exploit the inclusion ability of the cavity in its interaction with a substrate and mimic the binding pocket of an enzyme (Figure 1 a).Second, the metal can be encapsulated inside the cavity to study the effect of confinement on its coordination sphere and chemical properties; this arrangement mimics the environment of a metal buried deeply within a folded protein (Figure 1 b).The first kind of design has been widely studied, often with the attachment of a metal-ligand unit through a single linkage.[3] Such structures can be used in a multitude of applications, for example, in catalysis.[4] However, for the metal center to be fixed directly above the cavity, double linkage of the metal was necessary. In the resulting so-called metal-capped CDs, [5,6] the metal ion is located right on top of the CD cavity.[7] The deepest position in which the metal has been placed so far intercepts the plane defined by the C-6 atoms of the sugar units. [8,9] This metal position leaves the cavity available for the inclusion of guests. The cavity can thus serve as a host for substrates (the interaction of which with the metal center can lead to an acceleration of the reaction rate [10] in analogy with an enzymatic reaction), as a probe for ligand exchange, [8] or as a second coordination sphere through C À H···X À M interactions. [11] For metallocyclodextrins of the second kind, in which the metal center occupies the middle of the cavity like an included guest, typically at the level of the H-5 atoms, only noncovalent inclusion complexes of metal ions have been described so far. Their electrochemical properties have been studied thoroughly, and electron transfer is thought not to involve the included complex, but the free portion of nonincluded metallic guest ions.[12] In other words, no studies on cyclodextrin complexes in which the metal ion is forced through covalent bonding to be included deep inside the Figure 1. In a metal-capped cyclodextrin, the cavity interacts either a) with the substrate or b) with the metal, depending on the depth of inclusion....

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Section: Methodsmentioning

confidence: 96%

NHC‐Capped Cyclodextrins (ICyDs): Insulated Metal Complexes, Commutable Multicoordination Sphere, and Cavity‐Dependent Catalysis

Guitet¹,

Zhang²,

Marcelo³

et al. 2013

Angew Chem Int Ed

138

117

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“…The first examples of the relevant cycloisomerisation of N‐tethered 1,6‐enynes into aza‐bicyclo[4.1.0]heptenes were described by Fürstner11 (PtCl 2 as the catalyst) and Echavarren12 (Ph 3 PAuCl as the catalyst). Later, the use of chiral complexes of platinum, gold, rhodium or iridium allowed elaboration of asymmetric versions of this reaction 10,13. Although applications in organic synthesis remain scarce,14 especially noteworthy are the formal synthesis of streptorubin B15 and the enantioselective synthesis of the antidepressant drug candidate GSK1360707 16…”

Section: Resultsmentioning

confidence: 99%

Access to New Endoperoxide Derivatives by Electrochemical Oxidation of Substituted 3‐Azabicyclo[4.1.0]hept‐4‐enes

Nuter

Dimé

Chen

et al. 2015

Chemistry A European J

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“…131 Recently, Evans et al developed a rhodium-catalyzed cycloisomerization reaction of alkenylidene cyclopropanes, leading to 1,5-diene structures, contrary to most cycloisomerization reactions that lead to 1,4-diene structures. 132 Furthermore, this process shows very good cis-3,4-diastereoselectivity on the THF (Scheme 40).…”

Section: Thf Synthesis By C-c Bond Formation 1 Cycloisomerizatimentioning

confidence: 98%

Recent advances in the synthesis of tetrahydrofurans and applications in total synthesis

et al. 2016

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Mousseron. His research interests include the total synthesis of oxygenated cyclic and non cyclic metabolites of polyunsaturated fatty acids, mainly leukotrienes, iso-, phyto-and neuroprostanes, as well as dihydroxylated PUFAs and more recently lipophenols and the understanding of the role of such bioactive lipids and lipophenols by developing collaborations with chemists, biochemists, biologists and clinicians across the world. Jean-Marie Galano studied chemistry at Paul Cézanne Université Marseille and obtained his PhD under the supervision of Honoré Monti in 2001. He then moved to the University of Oxford to pursue a postdoctoral fellowship with David H. Hodgson on the development of new methods for the total synthesis of natural products. In October 2005 he joined the CNRS as a Chargé de Recherche at Université of Montpellier. His research focuses on the total synthesis and discovery of new lipid metabolites, and to discover their potential implications in human health. AbstractMany natural products contain tetrahydrofuran (THF) moieties. Those molecules, often biologically active, may be structurally diverse, e.g. cis or trans THF, mono-, di-, tri-or tetrasubstituted on the furan ring. Thus, the construction of THF is of great interest for the community of organic chemists; especially in developing new methodologies, and applying them in the total synthesis of natural products. The aim of this review is to report recent advances in the field of THF synthesis, as well as the application of these methods to the synthesis of bioactive compounds.

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Enantioselective, transition metal catalyzed cycloisomerizations

Cited by 234 publications

References 167 publications

NHC‐Capped Cyclodextrins (ICyDs): Insulated Metal Complexes, Commutable Multicoordination Sphere, and Cavity‐Dependent Catalysis

NHC‐Capped Cyclodextrins (ICyDs): Insulated Metal Complexes, Commutable Multicoordination Sphere, and Cavity‐Dependent Catalysis

Access to New Endoperoxide Derivatives by Electrochemical Oxidation of Substituted 3‐Azabicyclo[4.1.0]hept‐4‐enes

Recent advances in the synthesis of tetrahydrofurans and applications in total synthesis

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