176098-24-1Relevant articles and documents
An atom-economic synthesis of bicyclo[3.1.0]hexanes by rhodium N-heterocyclic carbene-catalyzed diastereoselective tandem hetero-[5 + 2] cycloaddition/claisen rearrangement reaction of vinylic oxiranes with alkynes
Feng, Jian-Jun,Zhang, Junliang
supporting information; experimental part, p. 7304 - 7307 (2011/06/27)
The first synthetic application of a vinylic oxirane as a heteroatom-containing five-atom component in transition-metal-catalyzed cycloaddition reactions is reported. A new, efficient, diastereoselective tandem intramolecular hetero-[5 + 2] cycloaddition/Claisen rearrangement of vinylic oxirane-alkyne substrates that uses a rhodium NHC complex and provides strategically novel, atom-economic, regiospecific, and diastereoselective access to [3.1.0] bicyclic products has been developed.
Stereocontrolled preparation of stereocomplementary regioisomeric tricarbonyliron complexes in enantiopure form
Anson, Christopher E.,Dave, Gaurang,Stephenson, G. Richard
, p. 2273 - 2281 (2007/10/03)
The use of ultrasound to form ferralactone complexes from an enantiomerically pure allylic epoxide with an adjacent hydroxymethyl substituent affords a pair of stereocomplementary isomers that offer a regioconvergent route to the same chiral pentadienyliron complex. The enantiomeric purity, CD properties, and absolute configurations of intermediate η4-diene complexes are reported, and X-ray diffraction analysis of a pair of rearranged ferralactone complexes establishes their relative stereochemistries, and confirms their absolute stereochemistries. (C) 2000 Elsevier Science Ltd.
1,5-Asymmetric induction of chirality: Diastereoselective addition of organoaluminium reagents and allylstannanes into aldehyde groups in the side-chain of π-allyltricarbonyliron lactone complexes
Ley, Steven V.,Burckhardt, Svenja,Cox, Liam R.,Meek, Graham
, p. 3327 - 3337 (2007/10/03)
π-Allyltricarbonyliron lactone complex 5, bearing an aldehyde group in the side-chain, can be easily prepared from commercially available (2E,4E)-ethyl hexadienoate and reacts with organoaluminium and allylstannane nucleophiles to afford secondary alcohols. In analogy with the corresponding ketone-substituted complexes, the lactone tether acts via the Fe(CO)3 moiety as a source of asymmetric induction. The levels of diastereoselectivity are generally reduced, however, compared with those obtained using ketone complexes. This can be attributed, at least in part, to the carbonyl appendage adopting both s-cis and s-trans conformations. The level of 1,5-asymmetric induction is strongly dependent upon the nature of the nucleophile in the case of the organoaluminium reactions and upon the reaction temperature in the case of BF3-mediated addition of allylstannanes into the aldehyde group.
Reactivity of Lysine Moieties toward γ-Hydroxy-α,β-unsaturated Epoxides: A Model Study on Protein-Lipid Oxidation Product Interaction
Lederer, Markus O.
, p. 2531 - 2537 (2007/10/03)
Epoxyols are generally accepted as crucial intermediates in lipid oxidation. The reactivity of γ-hydroxy-α,β-unsaturated epoxides toward lysine moieties is investigated, employing trans-4,5-epoxytrans-2-hexen-1-ol (EH) as a model substrate and propylamine or N2-acetyl-L-lysine 4-methylcoumar-7-ylamide (AcLys-MCA) as model reagents for protein-bound lysine. Independent syntheses are reported for EH and AcLys-MCA. Reaction of the amine components with EH in THF yields 4-(propylamino)-trans-2-hexene-1,5-diol and N2-acetyl-N6-(1,5-dihydroxy-trans-2-hexen-4-yl)-L-lysine 4-methylcoumaryl-7-amide, respectively. Unequivocal structural characterization of the products prove the epoxy ring cleavage to proceed by a true SN2 mechanism. Incubation of EH with propylamine and AcLys-MCA in aqueous medium at 37 °C shows the turnover to decrease with lower pHs. From reaction of EH (100 mM) with AcLys-MCA (50 mM) under physiological conditions (pH 7.4), 3% of the lysine moieties can be identified in the form of N2-acetyl-N6-(1,5-dihydroxy-trans-2-hexen-4-yl)-L-lysine 4-methylcoumar-7-ylamide after 24 h.
Diastereoselective additions to aldehyde groups in the side-chain of π-allyltricarbonyliron lactone complexes
Ley, Steven V.,Meek, Graham
, p. 317 - 318 (2007/10/03)
π-Allyltricarbonyliron lactone complexes containing aldehyde groups adjacent to the allyl system undergo addition reactions with a variety of organoaluminium reagents in moderate to excellent diastereoselectivity.
