. "GA203/04/0487" . . . . . . "1"^^ . "Attempts to transfer the chirality in the course of the reactions of axially-chiral aminocarbene complexes of chromium have shown that, due to the steric interactions, the reactions typical for aminocarbene complexes did not proceed at all. Alternatively"@en . "1"^^ . . . . "1. Bude rozpracov\u00E1na n\u00E1mi nov\u011B vyvinut\u00E1 chemie aminokarbenov\u00FDch komplex\u016F chr\u00F3mu, a) Studium p\u0159enosu chirality p\u0159i fotochemick\u00FDch reakc\u00EDch nov\u00FDch enantiomern\u011B \u010Dist\u00FDch axi\u00E1ln\u011B chir\u00E1ln\u00EDch aminokarbenov\u00FDch komplex\u016F s iminy a alkeny p\u0159isp\u011Bje k pozn\u00E1n\u00ED mechanismu t\u00E9to reakce a umo\u017En\u00ED p\u0159\u00EDpravu chir\u00E1ln\u00EDch cyklobutanon\u016F a b-lakt\u00E1m\u016F. b) Bude provedena podrobn\u00E1 studie Pd- katalyzovan\u00E9 allylov\u00E9 substituce s vyu\u017Eit\u00EDm aniont\u016F Fischerov\u00FDch karbenov\u00FDch komplex\u016F Cr a W jako nukleofilu. Pozornost bude v\u011Bnov\u00E1na p\u0159edev\u0161\u00EDm rozd\u00EDlu reaktivity alkoxy- a aminokarbenov\u00FDch komplex\u016F, enantioselektivn\u00ED katal\u00FDze, katal\u00FDze jin\u00FDmi kovy ne\u017E palladiem (p\u0159edev\u0161\u00EDm Mo a W, kter\u00E9 vykazuj\u00ED opa\u010Dnou regioselektivitu ne\u017E Pd) a reaktivit\u011B z\u00EDskan\u00FDch nenasycen\u00FDch karbenov\u00FDch komplex\u016F. V\u00FDsledky budou vyu\u017Eiteln\u00E9 pro p\u0159\u00EDpravu substituovan\u00FDch nenasycen\u00FDch karbenov\u00FDch komplex\u016F, kter\u00E9 se uk\u00E1zaly jako vhodn\u00E9 v\u00FDchoz\u00ED l\u00E1tky pro p\u0159\u00EDpravu n\u011Bkter\u00FDch polycyklick\u00FDch syst\u00E9m\u016F (nap\u0159. steroidy). 2. Bude provedena elektrochemick\u00E1 (p\u0159\u00EDpadn\u011B" . . "Preparation, reactivity and electrochemistry of new aminocarbene complexes of chromium and iron"@en . "0"^^ . . . . . "P\u0159\u00EDprava, reaktivita a elektrochemie nov\u00FDch typ\u016F aminokarbenov\u00FDch komplex\u016F chromu a \u017Eeleza" . "P\u0159i pokusech o p\u0159enos chirality p\u0159i reakc\u00EDch axi\u00E1ln\u011B chir\u00E1ln\u00EDch karbenov\u00FDch komplex\u016F se uk\u00E1zalo, \u017Ee vlivem sterick\u00FDch z\u00E1bran reakce typick\u00E9 pro aminokarbenov\u00E9 komplexy chromu bu\u010F neprob\u00EDhaj\u00ED v\u016Fbec, nebo prob\u00EDhaj\u00ED a\u017E za podm\u00EDnek, kdy doch\u00E1z\u00ED k jejich race"@cs . . "Neuvedeno."@en . "http://www.isvav.cz/projectDetail.do?rowId=GA203/04/0487"^^ . . "19"^^ . . "2007-10-16+02:00"^^ . "19"^^ . "1. New chemistry of chromium aminocarbene complexes developed in our laboratory will be exploited. a) Study of the chirality transfer in the photochemical reactions of new enantiomerically pure axially chiral aminocarbene complexes of chromium with alkenes and imines will contribute to the general knowledge of this reaction. Possibility to synthesise chiral cyclobutanones and b-lactams will be also attempted. b) Detailed study of Pd-catalyzed allylic substitution involving Fischer carbenes as nucleophiles will be performed. Especially the difference in the reactivity between alkoxy- and aminocarbenes, enantioselective catalysis, catalysis with different metals (especially Mo and W, which exhibit opposite regioselectivity compared to Pd) and the reactivity of obtained carbenes will be addressed. The results can be used for the preparation of substituted unsaturated carbene complexes useful for the preparation of some polycyclic systems (e.g. steroids). 2. The basic electrochemical"@en . . . . .