Rhodium‐Catalyzed Enantioselective Nucleophilic Fluorination: Ring Opening of Oxabicyclic Alkenes

Zhu, Jianbo; Tsui, Gavin Chit; Lautens, Mark

doi:10.1002/anie.201207356

Cited by 128 publications

(47 citation statements)

References 94 publications

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“…These manifestations could be especially important for catalytic fluorination processes, where catalysts, particularly metal fluorides, are exposed to an excess of a HF source [30][31][32][33]. However, the influence of the metal and/or the ligand on this moiety is still unclear.…”

Section: Introductionmentioning

confidence: 99%

Transition metal bifluorides

Nahra

Brill

Gómez‐Herrera

et al. 2016

Coordination Chemistry Reviews

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A c c e p t e d M a n u s c r i p t HighlightsSince their discovery four decades ago, transition metal bifluoride complexes have long been considered as unwanted byproducts, a necessary evil, on the route to access fluoride complexes. Until recently, reports on this chemistry almost always presented these complexes as a fluke discovery. However, with the recent increase in reports and applications involving such species, a renewed interest in these complexes has been observed. Most of the work done in this area, so far, has been directed toward the synthesis and quite challenging characterization of these complexes, yet mostly neglecting the behavior of such species and their influence on catalytic processes. The aim of this work is to present a summary of the various preparation methods, characterization techniques and applications of reported transition metal bifluoride complexes. It is our hope that by centralizing all information available on such species, future efforts aimed at exploiting the full potential of transition metal bifluoride species can be facilitated.

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Section: Introductionmentioning

confidence: 99%

Transition metal bifluorides

Nahra

Brill

Gómez‐Herrera

et al. 2016

Coordination Chemistry Reviews

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“…This pioneering work has been regarded as a landmark in rapid access to chiral building blocks, as the resulting allylic compounds are important structural motifs in medicinal chemistry12. Since then, various nucleophiles were applied to this catalytic system including oxygen nucleophiles13, nitrogen nucleophiles14, sulfur nucleophiles15, carbon nucleophiles16 and halogen atoms17.…”

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confidence: 99%

Mechanism, reactivity, and regioselectivity in rhodium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes: a DFT Investigation

Zhang

Gao

et al. 2017

Sci Rep

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The origin of the enantio- and regioselectivity of ring-opening reaction of oxabicyclic alkenes catalyzed by rhodium/Josiphos has been examined using M06-2X density functional theory(DFT). DFT calculations predict a 98% ee for the enantioselectivity and only the 1,2-trans product as one regio- and diastereomer, in excellent agreement with experimental results. The solvent tetrahydrofuran(THF) plays a key role in assisting nucleophilic attack. Orbital composition analysis of the LUMO and the NPA atomic charge calculations were conducted to probe the origins of the regioselectivity. The orbital composition analysis reveals two potential electrophilic sites of the Rh–π-allyl intermediate M3 and the NPA atomic charges demonstrate that Cα carries more positive charges than Cγ, which suggests that Cα is the electrophilic site.

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“…Fluorination of terminal allylic electrophiles occurred regioselectively to give branched allylic fluorides in high yield. The reported substrate scope for terminal allylic electrophiles bound to a methylene group is similar to that of 3 catalyzed by rhodium and a chiral bisphosphine [27]. Nguyen later reported that a rhodium(I) catalyst efficiently catalyzes hydrofluorination of vinylepoxides with Et 3 N(HF) 3 to yield allylic fluorohydrins [28].…”

Section: Allylic Fluoride Synthesismentioning

confidence: 87%

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

Campbell

Hoover

Ritter

2014

Topics in Organometallic Chemistry

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The development of new C-F bond forming reactions from organotransition metal complexes has played a key role in advancing the field of fluorination chemistry and has allowed for improved access to fluorinated organic molecules of interest in medicine, materials, and agrochemicals. In this review, we describe the development of transition metal-mediated and metal-catalyzed fluorination methods over the past decade. Special attention is paid to the variety of organometallic mechanisms by which C-F bond formation can occur and the strengths and limitations of different approaches.

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Rhodium‐Catalyzed Enantioselective Nucleophilic Fluorination: Ring Opening of Oxabicyclic Alkenes

Abstract: for single-crystal X-ray structure analysis, and Solvias AG for the generous gift of chiral ligands. J.Z. thanks SIOC for a postdoctoral fellowship. G.C.T. thanks NSERC for a postgraduate scholarship.Supporting information for this article is available on the WWW under http://dx.

Cited by 128 publications

References 94 publications

Transition metal bifluorides

Transition metal bifluorides

Mechanism, reactivity, and regioselectivity in rhodium-catalyzed asymmetric ring-opening reactions of oxabicyclic alkenes: a DFT Investigation

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

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