Fluorinative ring-expansion of cyclic ethers using p-iodotoluene difluoride. Stereoselective synthesis of fluoro cyclic ethers

Inagaki, Tomotake; Nakamura, Yutaka; Sawaguchi, Masanori; Yoneda, Norihiko; Ayuba, Shinichi; Hara, Shoji

doi:10.1016/s0040-4039(03)00841-4

Cited by 41 publications

(18 citation statements)

References 20 publications

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“…A unique fluorinative ring expansion of O ‐heterocycles 16 , having an iodomethylene unit adjacent to the ring oxygen, was reported by Hara and co‐workers (Scheme a) . Treatment of 16 with the hypervalent iodine(III) fluoro reagent 10 , which needed to be activated through H‐bonding by the addition of NEt 3 ⋅ 5 HF, resulted in the rapid formation of ethers 17 that bear an additional C atom within the cyclic array.…”

Section: Halogenations Using Hypervalent Iodine(iii) Reagentsmentioning

confidence: 81%

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Advances in Iodine(III)‐Mediated Halogenations: A Versatile Tool to Explore New Reactivities and Selectivities

Arnold

Ulmer

Gulder

2016

Chemistry A European J

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Within the repertoire of organic chemical transformations, the halogenation of substrates is among the most versatile, reliable, and broadly applicable reactions. Although a multitude of different methods are known today, there is still a huge demand for novel and, in particular, catalytic halogenation methods that exhibit new reactivities and selectivities. The class of hypervalent iodanes meets exactly these needs and thus offers a great opportunity to fuel this highly desirable direction within the field of halogenation chemistry. This Concept gives a short overview of recent examples focusing on selective and/or mechanistically unusual halogenations.

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Section: Halogenations Using Hypervalent Iodine(iii) Reagentsmentioning

confidence: 81%

“… a) Hypervalent iodine(III)‐triggered ring expansion of O ‐containing heterocycles 16 ; b) the postulated mechanism of this transformation …”

Section: Halogenations Using Hypervalent Iodine(iii) Reagentsmentioning

confidence: 99%

Advances in Iodine(III)‐Mediated Halogenations: A Versatile Tool to Explore New Reactivities and Selectivities

Arnold

Ulmer

Gulder

2016

Chemistry A European J

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“…Hara et al [227] have focused on the stereoselective synthesis of fluorinated cyclic ethers, since their derivatives seemed to be involved in biochemical mechanisms. They have reported the ring expansion of oxetanes using 4-iodotoluene difluoride.…”

Section: Nucleophilic Attacksmentioning

confidence: 99%

Four‐Membered Heterocycles: Structure and Reactivity

Rousseau

Robin

2011

Modern Heterocyclic Chemistry

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“…Fluorinative ring expansions were also performed in its pres ence, with a mechanistic pathway involving the addition of a fluoride ion to an oxonium ion formed by cyclization of an unstable hypervalent iodinated intermediate [17]. In 2000, Sawaguchi et al reported the fluorocyclization of carboxylic acids and alcohols featuring a mechanistically related fluoride attack for the CF bondforming event [18].…”

Section: Mini-review | Wilkinson Salmon and Gouverneurmentioning

confidence: 99%

Developments in Fluorocyclization Methodologies

2009

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Fluorinated organic compounds constitute a significant proportion of medicines marketed today. Since heterocycles are submotifs frequently encountered in lead compounds, the corresponding fluorinated molecules that possess coupling functional groups to increase structural complexity are sought-after building blocks, especially those with stereogenic elements. To access fluoro-heterocycles, fluorocyclizations constitute an important category of reactions that permit multiple bond construction in one pot. Reactions featuring both nucleophilic and electrophilic sources of fluorine have proved valuable for the delivery of fluorinated carbo- and heterocycles. Mechanistically, two scenarios have been validated with the fluorination occurring either prior to or after the cyclization event. Fluorinated biologically active molecules prepared by employing a fluorocyclization protocol are rare, with two notable exceptions being the synthesis of fluorogypsetin and fluorobrevianamide E. Various levels of diastereocontrol were obtained with best results observed when the cyclization step precedes the fluorination. To date, asymmetric fluorocyclizations have not been explored, with the exception of a Nazarov fluorination process. In essence, this process features a catalytic asymmetric cyclization followed by a diastereoselective fluorination. Asymmetric fluoroheterocyclizations are, however, not known. For this methodology to serve medicinal chemistry, conceptual advances are essential to access fluorinated pharmacophores with programmable stereocontrol as and when necessary.

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Fluorinative ring-expansion of cyclic ethers using p-iodotoluene difluoride. Stereoselective synthesis of fluoro cyclic ethers

Cited by 41 publications

References 20 publications

Advances in Iodine(III)‐Mediated Halogenations: A Versatile Tool to Explore New Reactivities and Selectivities

Advances in Iodine(III)‐Mediated Halogenations: A Versatile Tool to Explore New Reactivities and Selectivities

Four‐Membered Heterocycles: Structure and Reactivity

Developments in Fluorocyclization Methodologies

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