Aldehydes zinc compound

Ethylhexanol is usually produced by subsequent aldolization of butyraldehyde produced in the oxo reaction followed by hydrogenation of the intermediate unsaturated aldehyde.89 In Esso s Aldox process, however, in situ aldol condensation is effected by suitable promoters.11 Magnesium ethoxide and soluble zinc compounds are recommended to promote controlled aldolization during the oxo reaction. The Shell variant uses potassium hydroxide. Serious disadvantages (mixed aldolization with the branched aldehyde, problems associated with recycling of the additives), however, prevented wider use of the Aldox process. 

Various hyposulphite compounds are used for industrial purposes including stable aldehyde compounds. Of these the formaldehyde compound (Formosul) is tie most important, since it is the reducing agent almost universally employed in applying vat dyes by printing methods to textile materials. The less stable sodium hydrosulphite is used in dyeing with vat dyes. Stable zinc compounds (Rongalite) are also on the market. 

Transformations involving chiral catalysts most efficiently lead to optically active products. The degree of enantioselectivity rather than the efficiency of the catalytic cycle has up to now been in the center of interest. Compared to hydrogenations, catalytic oxidations or C-C bond formations are much more complex processes and still under development. In the case of catalytic additions of dialkyl zinc compounds[l], allylstan-nanes [2], allyl silanes [3], and silyl enolethers [4] to aldehydes, the degree of asymmetric induction is less of a problem than the turnover number and substrate tolerance. Chiral Lewis acids for the enantioselective Mukaiyama reaction have been known for some time [4a - 4c], and recently the binaphthol-titanium complexes 1 [2c - 2e, 2jl and 2 [2b, 2i] have been found to catalyze the addition of allyl stannanes to aldehydes quite efficiently. It has been reported recently that a more active catalyst results upon addition of Me SiSfi-Pr) [2k] or Et2BS( -Pr) [21, 2m] to bi-naphthol-Ti(IV) preparations. 

Organozinc addition reactions to unsaturated systems lead to an intermediate zinc compound which is in most cases further hydrolyzed to give the corresponding protonated organic compound. This intermediate can also be trapped by reaction with electrophiles (see Electrophile) (E+) such as aldehydes, acyl chlorides, organic halides, silyl halides, and so on. Depending on the nature of the electrophile (see... 

In the presence of MgX2, organo-cadmium and -zinc compounds add smoothly to imines derived from aromatic aldehydes and arylamines. Yields are very low with isolated alkyl-cadmiums or -zincs which lack a Lewis acid promoter (equation 48). ... 

Chiral phthalides are synthesized from an o-iodobenzoic ester that forms a zinc compound. With a P-chiral diphosphinocobalt complex 50 present the addition to aldehydes follows an asymmetric course. ... 

Reductions. The reduction of carbonyl compounds with PMHS requires promoters. These include 2,8,9-trimethyl-l-phospha-2,5,8,9-tetraazabicyc1o[3.3.3]undecane and zinc compounds. - Conjugated aldehydes are converted to allylic alcohols. ... 

The role of stoichiometric amount of zinc compounds in the aldol reaction was studied 30 years ago (107). The first study of asymmetric zinc-catalyzed aldol reaction was carried out by Mukaiyama and co-workers the chiral zinc catalyst was prepared from diethylzinc and chiral sulfonamides and was effective in the reaction of ketene silyl ethers with aldehydes (108). Among the subsequent studies on zinc-catalyzed aldol reactions, Trost s group gave important contribution to zinc/prophenol ligand complexes (109,110). The chiral dinuclear zinc catalyst promotes the direct aldol reaction of ketones, including a-hydroxyketones, and aldehydes with excellent enantioselectivity (Scheme 17). It is proposed that one zinc metal coordinated different substrates to form zinc enolate, and another zinc metal center provided the bridge between the interaction of donor and acceptor. 

Seebach and his co-workers have also reported the enantioselective conjugate addition of chiral organo-lithium, -copper, and -zinc compounds to a,P-unsaturated aldehydes using the chiral methoxyamine (116) as co-solvent. ... 

Von dem Bussche-Htiimefeld JL, Seebach D (1992) Enantioselective preparation of sec. Alcohols from aldehydes and diaUcyl zinc compounds, generated in situ from Grignard reagents, using substoichiometric amounts of TADDOL-titanates. Tetrahedron 48 5719-5730... 

The 2-functionalized dienes (194) are also available by the reaction of the zinc derivative (193) with aldehydes, the zinc compound (193) being formed by the reaction of (192) with zinc. Corey and Hoover have developed the sulphoxide... 

The simple prototype can, for instance, be converted into iodide 276, which as a diorganic zinc compound can undergo a reagent-controlled diastereoselective addition to aldehydes providing the sy -alcohols 279-syn with high selectivity [94]. 

A diastereoselective addition of an organotitanium-zinc compound to an aldehyde function to give the E-ejco-alcohol has been part of the synthesis of an iron containing 5-hydroxy-(6 , 8Z, 1IZ, 14Z)-icosatetraenoic acid (5-HETE) analog. ... 

Alkyl Isoquinolines. Coal tar contains small amounts of l-methylisoquinoline [1721-93-3] 3-methylisoquinoline [1125-80-0] and 1,3-dimetliylisoquinoline [1721-94-4J. The 1- and 3-methyl groups are more reactive than others in the isoquinoline nucleus and readily oxidize with selenium dioxide to form the corresponding isoquinoline aldehydes (174). These compounds can also be obtained by the hydrolysis of the dihalomethyl group. The 1- and 3-methyhsoquinolines condense with benzaldehyde in the presence of zinc chloride or acetic anhydride to produce 1- and 3-styryhsoquinolines. Radicals formed by decarboxylation of carboxyUc acids react to produce 1-aIkyhsoquinolines. 

In similar work, CF3CCI2CO2CH3 yields methyl a-trifluoromethyl-a,(i-un-saturated carboxylates when reacted with a zinc-copper couple, aldehydes, and acetic anhydride [67] (equation 55). This methodology gives (Z)-a-fluoro-a- -un-saturated carboxylates from the reaction of carbonyl compounds with CFCI2CO2CH3 and zinc and acetic anhydride [6 ]. 

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