Chelate Complexes with the P=O-Double Bond - A New Concept for Asymmetric Synthesis

Schräder, Thomas; Kirsten, Christian; Herm, Michael

doi:10.1080/10426509908546207

Cited by 11 publications

(5 citation statements)

References 7 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Exclusive formation of the trans -decalin 11 requires overlap of an equatorally oriented orbital with the σ* orbital of the C−Cl bond. The cyclization stereochemistry is consistent with forming a pyramidal nitrile anion in which internal chelation between the alkoxy lithium cation and the π-electrons of the nitrile 7b, defines the stereochemistry at the nitrile-bearing carbon.…”

mentioning

confidence: 74%

Metalated Nitriles: Cation-Controlled Cyclizations

et al. 2007

View full text Add to dashboard Cite

Judicious choice of cation allows the selective cyclization of substituted gamma-hydroxynitriles to trans- or cis-decalins and trans- or cis-bicyclo[5.4.0]undecanes. The stereoselectivities are consistent with deprotonations generating two distinctly different metalated nitriles: an internally coordinated nitrile anion with BuLi, and a C-magnesiated nitrile with i-PrMgCl. Employing cations to control the geometry of metalated nitriles permits stereodivergent cyclizations with complete control over the stereochemistry of the quaternary, nitrile-bearing carbon.

show abstract

mentioning

confidence: 74%

Metalated Nitriles: Cation-Controlled Cyclizations

et al. 2007

View full text Add to dashboard Cite

show abstract

“…Non covalent interactions are used in order to assemble designed building blocks. These assemblies have various applications such as microreactors [ 2 , 3 ], organic or anionic species sensors [ 4 , 5 ], and materials for optical and electroluminescent devices [ 6 , 7 , 8 ].…”

Section: Introductionmentioning

confidence: 99%

A Pyrene- and Phosphonate-Containing Fluorescent Probe as Guest Molecule in a Host Polymer Matrix

et al. 2013

View full text Add to dashboard Cite

New host-guest materials have been prepared by incorporation of a home-made organic probe displaying a pyrene motif and a phosphonate function into a regular amphiphilic copolymer. Using powder X-Ray diffraction, photoluminescence and FT-IR spectroscopy, we have been able to study the non-covalent interactions between the host matrix and the guest molecule in the solid state. Interestingly, we have shown that the matrix directs the guest spatial localization and alters its properties. Thanks to the comparison of pyrene vs. N-pyrenylmaleimide derivatives, the influence of the chemical nature of the guest molecules on the non-covalent interactions with the host have been studied. In addition, using polyethylene glycol as a reference host, we have been able to evidence a true matrix effect within our new insertion materials. The phosphonated guest molecule appears to be a novel probe targeting the hydrophilic domain of the host copolymer.

show abstract

“…Complexation of metals, particularly lithium, with the π-electrons of a nitrile provides a particularly effective method of stereocontrol in a diverse range of reactions . In the case of nitrile 8 , deprotonating with a lithium base in benzene is anticipated to favor tight association of the lithium cation with the nitrile π-electrons and the proximal acetal oxygen leading to the pyramidal nitrile 11 (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Metalated Nitriles: Chelation-Controlled Cyclizations to cis and trans Hydrindanes and Decalins

Fleming

Shook

et al. 2007

J. Org. Chem.

View full text Add to dashboard Cite

Chelation provides a powerful means of stereocontrol in alkylations of metalated nitriles. Doubly deprotonating a series of cyclic beta-hydroxynitriles triggers cyclizations that implicate metalated nitrile intermediates having configurations imposed by chelation with an adjacent, chiral lithium alkoxide. Identifying chelation as a general stereocontrol element explains several previously anomalous alkylations of metalated nitriles and provides a potential solution to the long-standing difficulty of synthesizing trans-hydrindanes. Employing chelation to control the metalated nitrile geometry permits selective cyclizations to cis and trans hydrindanes and decalins and provides key insight into the geometrical requirements of these demanding cyclizations.

show abstract

Chelate Complexes with the P=O-Double Bond - A New Concept for Asymmetric Synthesis

Cited by 11 publications

References 7 publications

Metalated Nitriles: Cation-Controlled Cyclizations

Metalated Nitriles: Cation-Controlled Cyclizations

A Pyrene- and Phosphonate-Containing Fluorescent Probe as Guest Molecule in a Host Polymer Matrix

Metalated Nitriles: Chelation-Controlled Cyclizations to cis and trans Hydrindanes and Decalins

Contact Info

Product

Resources

About