Stereomutation of Conformational Enantiomers of 9-Isopropyl-9-formylfluorene and Related Acyl Derivatives

Casarini, Daniele; Lunazzi, Lodovico; Mazzanti, Andrea

doi:10.1021/jo8008897

Cited by 3 publications

(2 citation statements)

References 19 publications

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“…[4] On the other hand, introduction of substituents at the C-9 methylene bridge of the fluorene unit requires base-mediated conditions, under which fluorene reacts with electrophiles. [5] As an alternative approach to synthesize the fluorene skeleton, an intramolecular aromatic carbenoid insertion can be regarded as a facile route to form a 5,6-bicyclic ring system. [6,7] In fact, this strategy was elegantly utilized in the preparation of (hetero)aromatic bicyclic ring systems, although the reaction efficiency fluctuates depending on the substrate type and reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

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Intramolecular Aromatic Carbenoid Insertion of Biaryldiazoacetates for the Regioselective Synthesis of Fluorenes

Kim

Ohk

Park

et al. 2011

Chemistry An Asian Journal

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The rhodium- or copper-catalyzed intramolecular aromatic carbenoid insertion of biaryldiazoacetates offers a convenient route to fluorene carboxylates with high yields. Whereas, thermal conditions provided a mixture of two regioisomeric products when substituted biaryldiazoacetates were employed as substrates. The developed catalytic conditions displayed an excellent level of regioselectivity, presumably owing to steric effects. The insertion mechanism was assumed to be an electrophilic aromatic substitution, which was supported by preliminary mechanistic studies. A chloro-substituted fluorene derivative was efficiently synthesized and utilized as a base-sensitive protecting group of amines.

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Section: Introductionmentioning

confidence: 99%

“…Presently, preparation of substituted fluorenes relies mainly on the Friedel–Crafts‐type reaction with rather low selectivity 4. On the other hand, introduction of substituents at the C‐9 methylene bridge of the fluorene unit requires base‐mediated conditions, under which fluorene reacts with electrophiles 5…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Aromatic Carbenoid Insertion of Biaryldiazoacetates for the Regioselective Synthesis of Fluorenes

Kim

Ohk

Park

et al. 2011

Chemistry An Asian Journal

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Steric effects which determine the conformational preferences and stereodynamic processes of aryl fluorenyl ketones

2009

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The stereodynamic processes and conformational preferences of two classes of aryl fluorenyl ketones have been investigated by means of dynamic NMR spectroscopy, DFT calculations and X-ray diffraction. When the aryl substituent has two hydrogens in the ortho positions, its rotation is independent of that of the fluorene ring. In contrast, if the two ortho hydrogens are replaced by the bulkier methyl groups (e.g. mesityl fluorenyl ketones), the motion of the aryl ring interacts with the fluorene, and the two rings rotate in a correlated manner.

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Stereochemical implications toward the total synthesis of aromatic belts

Golder

Zakharov

Jasti

2017

Pure and Applied Chemistry

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The synthesis of carbon nanotube (CNT) fragments has long captivated organic chemists, despite the simplistic, symmetric nature of the requisite achiral targets. Such molecules hold the potential to allow for the synthesis of homogeneous CNTs, rendering their properties more suitable for advanced applications in electronics and sensing. The [n]cycloparaphenylene family, comprised of molecules with para-linked phenyl rings in a contiguous macrocycles, represents a major landmark towards achieving absolute control of CNT architecture from the bottom-up. Attempts towards accessing the [n]cyclacene and [n]cyclophenacene families, both of which are comprised of double-stranded macrocyclic belts, have only recently been successful, however. These targets have been plagued by unstable, strained intermediates and stereochemical pitfalls that have largely thwarted accessing these fascinating structures. Herein, we disclose our synthetic strategy toward overcoming several stereochemical challenges en route to [n]cyclophenacenes via highly substituted [n]cycloparaphenylene precursors.

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Stereomutation of Conformational Enantiomers of 9-Isopropyl-9-formylfluorene and Related Acyl Derivatives

Cited by 3 publications

References 19 publications

Intramolecular Aromatic Carbenoid Insertion of Biaryldiazoacetates for the Regioselective Synthesis of Fluorenes

Intramolecular Aromatic Carbenoid Insertion of Biaryldiazoacetates for the Regioselective Synthesis of Fluorenes

Steric effects which determine the conformational preferences and stereodynamic processes of aryl fluorenyl ketones

Stereochemical implications toward the total synthesis of aromatic belts

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