Chromium complexes allyl

Table IV presents the results of the determination of polyethylene radioactivity after the decomposition of the active bonds in one-component catalysts by methanol, labeled in different positions. In the case of TiCU (169) and the catalyst Cr -CjHsU/SiCU (8, 140) in the initial state the insertion of tritium of the alcohol hydroxyl group into the polymer corresponds to the expected polarization of the metal-carbon bond determined by the difference in electronegativity of these elements. The decomposition of active bonds in this case seems to follow the scheme (25) (see Section V). But in the case of the chromium oxide catalyst and the catalyst obtained by hydrogen reduction of the supported chromium ir-allyl complexes (ir-allyl ligands being removed from the active center) (140) C14 of the...

The fact that pentacarbonyl carbene complexes react with enynes in a chemo-selective and regiospecific way at the alkyne functionality was successfully applied in the total synthesis of vitamins of the Kj and K2 series [58]. Oxidation of the intermediate tricarbonyl(dihydrovitamin K) chromium complexes with silver oxide afforded the desired naphthoquinone-based vitamin K compounds 65. Compared to customary strategies, the benzannulation reaction proved to be superior as it avoids conditions favouring (E)/(Z)-isomerisation within the allylic side chain. The basic representative vitamin K3 (menadione) 66 was synthesised in a straightforward manner from pentacarbonyl carbene complex 1 and propyne (Scheme 38). 

Highly diasteroselective and chemoselective reductions may be performed on the hydroxy functions of (r/6-arene)-tricarbonylchromium complexes. Treatment of the chromium-complexed benzylic alcohol 29 with triethylsilane and boron trifluoride etherate in dichloromethane at —78° to 0° gives only diastereomer 30 in 75% yield (Eq. 40).181 In a similar fashion, treatment of the complexed exo-allyl-endo-benzylic alcohol 31 with an excess of Et3SiH/TFA in dichloromethane at room temperature under nitrogen produces only the endo-aflyl product 32 in 92% yield after 1.5 hours (Eq. 41). It is noteworthy that no reduction of the isolated double bond occurs.182... 

Haloarene chromium tricarbonyl complexes are activated to nucleophilic attack by thiolate anions [58, 59]. High yields of the thioethers are obtained under liquiddiquid two-phase conditions, but optimum yields are achieved under soliddiquid conditions. In many cases the thioether is produced directly but, where the reaction mixture contains thioether and its chromium complex, the thioether can be isolated by degradation of the complex with iodine or an excess of the thiol. Both 1,2- and 1,4-dichlorobenzenes yield only monothioethers, even when an excess of thiolate anion is used. In contrast, 1,3-dichlorobenzenes produce a mixture of the mono- and dithioethers [59]. Aryl allyl thioethers have been produced under catalysed Heck reaction conditions from S-allyl thiocarbamates and iodobenzene [60]. 

The extensive organometallic chemistry of chromium, i.e. the hexacarbonyl and its derivatives, organochromium compounds without carbonyl ligands, cyanide and isocyanide complexes, alkene, allyl, diene, cyclopentadiene and arene derivatives, and complexes of a-donor carbon ligands, has been recorded in Chapters 26.1 and 26.2 of Volume 3 of Comprehensive Organometallic Chemistry .1 In the present section, chromium complexes... 

Fluxional behaviour, 73-allyl palladium complexes, 8, 371 Formamidinates, in chromium complexes, 5, 355 Formates, with Ru and Os half-sandwiches, 6, 483... 

Pauson-Khand cyclization3k 143 of tV-allyl (l-alkynyl)carbene complexes 134 (M = Cr, W R = Ph, Et R1 = H, Me) affords cyclopentenone derivatives 136144 via cobalt complexes 135145 (Scheme 53), as well as chromium complexes.146 Cyclopentenones also have been derived from 7V-diallyl(l-alkynyl)carbene complexes.39 Stable cobalt complexes of type 135 are obtained from O-allyl (l-alkynyl)carbene complexes. Interestingly, the last-named compounds do not form a cyclopentenone on heating instead, they form an enyne by elimination of M(CO)6 in a retro-Fischer reaction. 147... 

Castro and Kray have reduced the isomeric butenyl chlorides, using chromous sulfate (5). Again, allylic radicals were proposed as intermediates in the reaction. However, unlike the tin hydride reductions, 1-butene was obtained almost exclusively from each of the isomeric chlorides. The process has been described as occurring within a chromium complex. The preponderant formation of 1-butene from butenyl metal complexes has also been noted by others (12, 23, 46). 

An example, developed by our group, has been presented 3-chloro-propenyl pivalate, the new synthon we propose as a formal a-hydroxy allyl anion, and chromium(II) chemistry allow to achieve the formal diastereo- and enantio-selective a-hydroxyallylation of carbonyl compounds by applying a catalytic cycle based on an in situ produced Salen-chromium complex (Table 8.3). 

Oxidations. By using Phl=0 (in presence of KBr) as an oxidant, alcohols are oxidized to acids and ketones in water in excellent yields. When catalyzed by either poly(4-vinylpyridine)-supported sodium ruthenate or a (salen)chromium complex chemoselective oxidation of alcohols (e.g., allylic alcohols to alkenoic acids) occurs, which is contrary to the effect of (salen)manganese and (porphyrin)iron complexes (giving epoxy alcohols). ... 

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