Polyquinanes by [4 + 4] cycloaddition-transannular cyclization.

T A Ader; C A Champey; L V Kuznetsova; T Li; Y H Lim; D Rucando; S M Sieburth

doi:10.1021/ol016076x

Home/Archive/PubMed

PubMed · 11440570

Polyquinanes by [4 + 4] cycloaddition-transannular cyclization.

T A Ader·C A Champey·L V Kuznetsova·T Li·Y H Lim·D Rucando·S M Sieburth

View original source ↗Export metadata ↓

Abstract

[reaction: see text] Photocycloaddition of 2-pyridones yields a rigid polycyclic product containing a 1,5-cyclooctadiene. The cis isomer, with the alkenes in close proximity, undergoes a transannular reaction when treated with chlorine to give a polyquinane product. The chlorination reaction involves migration of an amide nitrogen and forms a single isomer, generating eight stereogenic centers in two steps.

Explore related subjects

Alkenes Crystallography, X-Ray Cyclization Heterocyclic Compounds Ketones Magnetic Resonance Spectroscopy Models, Chemical Molecular Conformation Molecular Structure Pyridones Stereoisomerism Structure-Activity Relationship Journal Article Research Support, Non-U.S. Gov't Research Support, U.S. Gov't, P.H.S.

Keep this discovery

Explore connections, maps & timelines

BibTeX RIS

T A Ader, C A Champey, L V Kuznetsova, T Li, Y H Lim, D Rucando, S M Sieburth. 2001-07-12. Polyquinanes by [4 + 4] cycloaddition-transannular cyclization.. https://doi.org/10.1021/ol016076x

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related citations

PubMed2007

Free energy profiles for monomer capture in Grubbs- and SHOP-type olefin polymerization catalysts: a constraint ab initio molecular dynamics study.

Density functional theory together with Car-Parrinello ab initio molecular dynamics simulation has been used to investigate the free energy profiles (FEP) of monomer capture in Grubbs- and SHOP-type olefin polymerization catalysts. The FEPs along the reaction coordinates at 300 K were determined directly by a point wise thermodynamic integration technique. Comparison between potential energy profile (PEP) and the FEP has been made. The results show that, for both catalysts, the PEP for the monomer ethylene uptake by the metal center is a typical Morse curve without energy barrier. However, a small barrier (1.8 kcal/mol for Grubbs catalyst and 2.4 kcal/mol for SHOP catalyst) exists on the FEP. The pi complexation energy on the FES at 300 K is higher by 10-12 kcal/mol over that on the PES. The differences between FES and PES are due to entropy contribution. Slow growth simulations on the ethylene capture process show that the ethylene attacks the metal center by an asynchronous mode. This indicates that the forming of the pi-bonding between the metal and ethylene is initiated by electrophilic attack of the metal to one of the ethylene carbons.

Alkenes↗

PubMed2007

Theoretical study on the mechanism of the [2+1] thermal cycloaddition between alkenes and stable singlet (phosphino)(silyl)carbenes.

The mechanism and the origins of the stereocontrol observed in the reaction between differently substituted alkenes and stable (phosphino)(silyl)carbenes giving cyclopropanes have been studied computationally. These cyclopropanation reactions proceed via asynchronous concerted mechanisms involving early transition structures with a significant charge transfer from the carbene to the alkene moiety. The geometric features of these transition structures preclude a significant overlap between the orbitals required for secondary orbital interactions between the reactants. The stereoselectivity observed experimentally stems from favorable electrostatic and steric interactions between the reactants leading to the stereoisomers in which the phosphanyl and carbonyl or aryl groups are cis to each other.

Alkenes↗

PubMed2007

Single enantiomer epoxides by bromomandelation of prochiral alkenes.

A combination of mandelic acid and N-bromosuccinimide efficiently converts prochiral alkenes into a readily separable 1:1 mixture of the bromomandelates. The diastereomerically pure bromomandelates are then converted into a variety of enantiomerically pure products. Terminal alkenes are converted into enantiomerically pure epoxides. Cyclohexene is converted into enantiomerically pure cis-2-azidocyclohexanol and cis-2-phenylthiocyclohexanol.

Alkenes↗