<i>trans</i>-2-Tritylcyclohexanol as a Chiral Auxiliary in Permanganate-Mediated Oxidative Cyclization of 2-Methylenehept-5-enoates: Application to the Synthesis of <i>trans</i>-(+)-Linalool Oxide

Hazmi, Ali M. Al; Sheikh, Nadeem S.; Bataille, Carole J. R.; Al-Hadedi, Azzam A. M.; Watkin, Sam V.; Luker, Tim; Camp, Nicholas P.; Brown, Richard C. D.

doi:10.1021/ol502454r

Cited by 20 publications

(12 citation statements)

References 41 publications

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“…The racemic trans-2-tritylcyclohexanol (rac-3) was obtained from cyclohexene oxide through opening the epoxide ring with a trityl anion. The optically active 3, in both enantiomeric forms, has been obtained from the racemate via oxalate 8 and by employing the procedure previously described by Hazmi et al [29]. The reactions provided both diasteroisomers of 8, differing in the absolute configurations of the trans-2-tritylcyclohexanol moiety, denoted here as 8a ((1S,2R)) and 8b ((1R,2S)), respectively.…”

Section: Synthesismentioning

confidence: 99%

Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity

et al. 2020

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The cascade process of a dynamic chirality transmission from the permanent chirality center to the stereodynamic triphenylmethyl group has been studied for series of optically active trityl derivatives. The structural analysis, carried out with the use of complementary methods, enabled us to determine the mechanism of chirality transfer. The process of chirality transmission involves a set of weak but complementary electrostatic interactions. The induction of helicity in a trityl propeller is revealed by rising non-zero cotton effects in the area of trityl UV-absorption. The presence of an additional stereogenic center in close proximity to the trityl-containing stereogenic center significantly affects the sign and, to a lesser extent, magnitude of the respective cotton effects. Despite the bulkiness of the trityl, in the crystalline phase, the molecules under study strictly fill the space. In the crystal, molecules form aggregates stabilized by OH•••O hydrogen bonds. However, the presence of two trityl groups precludes formation of OH•••O hydrogen bonding. Additionally, the trityl group seems to be responsible for the formation of the solid solutions by e.g., racemates of trans- and cis-2-tritylcyclohexanol. Therefore, the trityl group acts as a supramolecular protective group, which in turn can be used in the crystal engineering.

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Section: Synthesismentioning

confidence: 99%

Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity

et al. 2020

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“…The (S) enantiomer was prepared according to the general procedure using (R,S)-13 (10 mol %) from 6-methyl-2methylenehept-5-en-1-ol (16). From a 14.3 mmol (2.00 g) scale bromochlorination employing (R,S)-13 (615 mg, 1.43 mmol) was isolated product (+)-21 in 82% yield (3.00 g) of 84% ee as a >20:1 mixture of constitutional isomers after purification by flash column chromatography (25 g silica gel, 5 to 20% ethyl acetate/hexanes gradient).…”

Section: (S)-(+)-2-(bromomethyl)-2-chloro-6-methylhept-5-en-1-ol (21)mentioning

confidence: 99%

Catalytic Chemo-, Regio-, and Enantioselective Bromochlorination of Allylic Alcohols

et al. 2015

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Herein we describe a highly chemo-, regio-, and enantioselective bromochlorination reaction of allylic alcohols, employing readily available halogen sources and a simple Schiff base as the chiral catalyst. The application of this interhalogenation reaction to a variety of substrates, the rapid enantioselective synthesis of a bromochlorinated natural product, and preliminary extension of this chemistry to dibromination and dichlorination are reported.

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“…119,120 Later on, the same team changed for the corresponding sodium counterion for the synthesis of trans-(+)-Linalool oxide. 121 Manganese oxide was more recently used by the group of Vanderwal for the M A N U S C R I P T…”

Section: Scheme 35 : Oxidative Cyclization In Cascade Catalyzed By Osmentioning

confidence: 99%

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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trans-2-Tritylcyclohexanol as a Chiral Auxiliary in Permanganate-Mediated Oxidative Cyclization of 2-Methylenehept-5-enoates: Application to the Synthesis of trans-(+)-Linalool Oxide

Cited by 20 publications

References 41 publications

Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity

Trityl-Containing Alcohols—An Efficient Chirality Transmission Process from Inductor to the Stereodynamic Propeller and their Solid-State Structural Diversity

Catalytic Chemo-, Regio-, and Enantioselective Bromochlorination of Allylic Alcohols

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

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