Reduction carbonyl methylenation step

The second step is a reduction of the carbonyl group (C=0) to a methylene group (CH2)... 

The two step acylation-reduction sequence is required Acylation of benzene puts the side chain on the ring with the correct carbon skeleton Clemmensen reduc tion converts the carbonyl group to a methylene group... 

Reduction to Alkanes. Carbonyl groups can be reductively deoxygenated to methylene functions if both of the two steps represented by Eqs. 1 and 2 proceed to completion. With aldehydes, this process leads to the transformation of the CHO group into a CH3 group. 

The three-step sequence used to convert enone 65 to miltirone (56) is shown in Scheme 5.7 and consists of, first, a Wolff-Kishner reduction to convert the C(5) carbonyl moiety into a methylene, followed by deprotection of the aryl methyl ethers and oxidation to an ortho-quinone using ceric ammonium nitrate. The physical and spectroscopic data of our synthetic miltirone are identical with those reported for the natural material. 

The Reduction Reactions. The object of the next three reactions (steps 4 to 6 in fig. 18.12a) is to reduce the 3-carbonyl group to a methylene group. The carbonyl is first reduced to a hydroxyl by 3-ketoacyl-ACP reductase. Next, the hydroxyl is removed by a dehydration reaction catalyzed by 3-hydroxyacyl-ACP dehydrase with the formation of a trans double bond. This double bond is reduced by NADPH catalyzed by 2,3-trans-enoyl-ACP reductase. Chemically, these reactions are nearly the same as the reverse of three steps in the j6-oxidation pathway except that the hydroxyl group is in the D-configuration for fatty acid synthesis and in the L-configuration for /3 oxidation (compare figs. 18.4a and 18.12a). Also remember that different cofactors, enzymes and cellular compartments are used in the reactions of fatty acid biosynthesis and degradation. 

Attempts have been made to mimic proposed steps in catalysis at a platinum metal surface using well-characterized binuclear platinum complexes. A series of such complexes, stabilized by bridging bis(diphenyl-phosphino)methane ligands, has been prepared and structurally characterized. Included are diplati-num(I) complexes with Pt-Pt bonds, complexes with bridging hydride, carbonyl or methylene groups, and binuclear methylplatinum complexes. Reactions of these complexes have been studied and new binuclear oxidative addition and reductive elimination reactions, and a new catalyst for the water gas shift reaction have been discovered. 

Reduction of carbonyl group to methylene via thioacetals In contrast to the Clemmensen reduction (section 6.4.3) and Wolff-Kishner reduction (section 6.4.4), this method does avoid treatment with strong acid or base but requires two separate steps. The first step is to convert the aldehyde or ketone into a thioacetal. The second step involves refluxing an acetone solution of the thioacetal over a Raney nickel. This reduction method is known as Mozingo reduction. Hydrazine can also be used in the second step. 

Fatty acid synthesis is essentially the reverse of this process. The process starts with the individual units to be assembled— in this case with an activated acyl group (most simply, an acetyl unit) and a malonyl unit (see Figure 22.2). The malonyl unit condenses with the acetyl unit to form a four-carbon fragment. To produce the required hydrocarbon chain, the carbonyl group is reduced to a methylene group in three steps a reduction,... 

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