Chromium carbonyls, reaction with

Chiral salen chromium and cobalt complexes have been shown by Jacobsen et al. to catalyze an enantioselective cycloaddition reaction of carbonyl compounds with dienes [22]. The cycloaddition reaction of different aldehydes 1 containing aromatic, aliphatic, and conjugated substituents with Danishefsky s diene 2a catalyzed by the chiral salen-chromium(III) complexes 14a,b proceeds in up to 98% yield and with moderate to high ee (Scheme 4.14). It was found that the presence of oven-dried powdered 4 A molecular sieves led to increased yield and enantioselectivity. The lowest ee (62% ee, catalyst 14b) was obtained for hexanal and the highest (93% ee, catalyst 14a) was obtained for cyclohexyl aldehyde. The mechanism of the cycloaddition reaction was investigated in terms of a traditional cycloaddition, or formation of the cycloaddition product via a Mukaiyama aldol-reaction path. In the presence of the chiral salen-chromium(III) catalyst system NMR spectroscopy of the crude reaction mixture of the reaction of benzaldehyde with Danishefsky s diene revealed the exclusive presence of the cycloaddition-pathway product. The Mukaiyama aldol condensation product was prepared independently and subjected to the conditions of the chiral salen-chromium(III)-catalyzed reactions. No detectable cycloaddition product could be observed. These results point towards a [2-i-4]-cydoaddition mechanism. 

The major developments of catalytic enantioselective cycloaddition reactions of carbonyl compounds with conjugated dienes have been presented. A variety of chiral catalysts is available for the different types of carbonyl compound. For unactivated aldehydes chiral catalysts such as BINOL-aluminum(III), BINOL-tita-nium(IV), acyloxylborane(III), and tridentate Schiff base chromium(III) complexes can catalyze highly diastereo- and enantioselective cycloaddition reactions. The mechanism of these reactions can be a stepwise pathway via a Mukaiyama aldol intermediate or a concerted mechanism. For a-dicarbonyl compounds, which can coordinate to the chiral catalyst in a bidentate fashion, the chiral BOX-copper(II)... 

By a photochemically induced elimination of CO, a chromium carbene complex with a free coordination site is generated. That species can coordinate to an alkyne, to give the alkyne-chromium carbonyl complex 4. The next step is likely to be a cycloaddition reaction leading to a four-membered ring compound 5. A subsequent electrocyclic ring opening and the insertion of CO leads to the vinylketene complex 6 ... 

The dissociation process should be enhanced by UV irradiation and inhibited by high CO pressure, whereas a reaction through an associative pathway should be unaffected by either. We carried out the corresponding experiments /38/, and found that the chromium carbonyl catalyzed water gas shift reaction is much faster with irradiation than without, and that it is inhibited by high CO pressure. Therefore it seems quite clear that this reaction takes place through a dissociative mechanism. 

Cycloproparenes do not form metal complexes with all transition metals. Reaction of cyclopropabenzene with diiron-nonacarbonyl yields polymer, while reaction with cyclopropanaphthalene leads to a stable product formed by metal and carbonyl insertion. Attempts to form cycloproparene-chromium complexes have also failed. ... 

Some important reactions of chromium hexacarbonyl involve partial or total replacements of CO ligands by organic moieties. For example, with pyridine (py) and other organic bases, in the presence of UV hght or heat, it forms various pyridine-carbonyl complexes, such as (py)Cr(CO)5, (py)2Cr(CO)4, (py)3Cr(CO)3, etc. With aromatics (ar), it forms complexes of the type, (ar)Cr(CO)3. Reaction with potassium iodide in diglyme produces a potassium diglyme salt of chromium tetracarbonyl iodide anion. The probable structure of this salt is [K(diglyme)3][Cr(CO)4lj. 

The relative amounts of the products depend on irradiation time, and the formation of the bis (triphenyl phosphite) chromium complex may be almost completely avoided by following the reaction with thin layer chromatography. The diastereoisomers are air stable and reasonably soluble in most organic solvents. Their infrared spectra exhibit a metal carbonyl band at 1925 cm 1 (i>co ester at 1729 cm"1) and a metal thiocarbonyl band at 1925 cm"1 (CH2C12 solution). The NMR spectra. I 5ch3 at 1.87 ppm 5co3CH3 at 3.77 ppm II 6ch3 at 1.77... 

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