Aldehydes dimerization with

Ugi five-center three-component reaction of pipecolinic acid and glycol aldehyde dimer with isocyanides gave a 1 1.7-2.1 diastereomeric mixture of l-oxoperhydropyrido[2,Tc][l,4]oxazine-9-carboxamides 397 (Scheme 35) <20010L4149>. Using CF3CH2OH as solvent is critical for the reaction. When 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid was employed, 1,3,4,6,11,11 a-hexahydro-[ l,4]oxazino[4,3+]isoquinoline-4-carboxarnide was formed. 

The key observation was that L-proline would catalyze the addition of a-hetero aldehydes to a-branched aldehydes such as 2 to give the aldol product 3 with high cnantio- and diastereocontrol. Even more exciting, in the absence of other acceptors the a-hetero aldehydes dimerize with high relative and absolute stereocontrol. Both alkoxy and silyloxy aldehydes worked efficiently. 

Pd-cataly2ed reactions of butadiene are different from those catalyzed by other transition metal complexes. Unlike Ni(0) catalysts, neither the well known cyclodimerization nor cyclotrimerization to form COD or CDT[1,2] takes place with Pd(0) catalysts. Pd(0) complexes catalyze two important reactions of conjugated dienes[3,4]. The first type is linear dimerization. The most characteristic and useful reaction of butadiene catalyzed by Pd(0) is dimerization with incorporation of nucleophiles. The bis-rr-allylpalladium complex 3 is believed to be an intermediate of 1,3,7-octatriene (7j and telomers 5 and 6[5,6]. The complex 3 is the resonance form of 2,5-divinylpalladacyclopentane (1) and pallada-3,7-cyclononadiene (2) formed by the oxidative cyclization of butadiene. The second reaction characteristic of Pd is the co-cyclization of butadiene with C = 0 bonds of aldehydes[7-9] and CO jlO] and C = N bonds of Schiff bases[ll] and isocyanate[12] to form the six-membered heterocyclic compounds 9 with two vinyl groups. The cyclization is explained by the insertion of these unsaturated bonds into the complex 1 to generate 8 and its reductive elimination to give 9. 

The general mechanistic features of the aldol addition and condensation reactions of aldehydes and ketones were discussed in Section 7.7 of Part A, where these general mechanisms can be reviewed. That mechanistic discussion pertains to reactions occurring in hydroxylic solvents and under thermodynamic control. These conditions are useful for the preparation of aldehyde dimers (aldols) and certain a,(3-unsaturated aldehydes and ketones. For example, the mixed condensation of aromatic aldehydes with aliphatic aldehydes and ketones is often done under these conditions. The conjugation in the (3-aryl enones provides a driving force for the elimination step. 

Tetramethyl-1,3-diphenyl-2,4,6,8-tetraoxaadamantane (163, R = CH3) is made either by dimerization of an a-formyl ketone, such as a-formyl-isobutyrophenone, (164, R = CH3) with sulfuric acid186 or by dimerization of the aldehyde (165) with borontrifluoride etherate.187 The structure of the product was determined by PMR.186... 

Aldehyde dimer may undergo dehydration to give an a, -unsaturated carbonyl. From butanal, the conjugated carbonyl is ethylpropylacrolein (Equation 2.10). The conjugated system of this material competes for coordination sites on the rhodium catalyst so that hydroformylation inhibition is observed.[8] The formation of 2-ethylhex-2-enal can be limited by minimizing the concentration of dimers. Dimers are removed along with the product in a liquid recycle separation system. 

Wiped-Film Evaporator/02 Reactivation of Catalyst. In this technology [38], spent or-ganophosphine-modified rhodium catalyst is first concentrated in a wiped-film evaporator where most of the organophosphine is removed. The rhodium concentrate is contacted with air to break down phosphido bridges in rhodium clusters. This air treated concentrate may then be used as a catalyst precursor. This procedure is suitable in circumstances where most of the aldehyde dimers, trimers and tetramers are sufficiently volatile to be removed in a wiped-film evaporator. 

The most characteristic and useful reaction is the dimerization with incorporation of certain nucleophiles. It is well-known that simple olefins coordinated by Pd2+ compounds undergo nucleophilic substitutions [Eq. (9)] or addition reactions [Eq. (10)] (16, 17). Water, alcohols, and carboxylic acids are typical nucleophiles which attack olefins to form aldehydes, ketones, vinyl ethers, and vinyl esters. 

In the case of 2-EH production, the aldehyde dimerizes or reacts with itself. Dimerize, remember, has the same Latin root -meros, as isomer, monomer, and polymer, and means part. A dimer is a chemical union of two molecules of the same compound.) The resulting Cs dimer is also an aldehyde that can be hydrogenated to give 2-EH. 

Aldol condensation. A misnomer from the contraction of Aldehyde and alcohol, but alcohol is a subsequent step. Aldol condensation involves the reaction of an aldehyde with itself or another aldehyde (dimerizing) in the presence of an alkaline catalyst. The resulting dimer is also an... 

When the oxidation of a primary alcohol with PCC results in the formation of an aldehyde, activated with an electron withdrawing group at the a-position sometimes, a stable dimeric hemiacetal is formed that is further oxidized to a dimeric ester.331 This reaction, that can also happen with other chromium-based reagents (see page 42), can be minimized by adjusting the reaction conditions. 

The aldehyde reacts with the starting alcohol, yielding a stable hemiacetal that can be further oxidized to a dimeric ester. The formation of the dimeric ester can be minimized by the use of high dilution and the slow addition of the alcohol to the oxidant, resulting in a reaction giving an optimized 5 2 ratio of aldehyde to dimeric ester. 

An antennal-specific aldehyde oxidase (AOX) of M. sexta (MsexAOX) was the next identified pheromone-degrading enzyme (Rybczynski el al., 1989). The activity of MsexAOX was visualized on non-denaturing PAGE, and was shown to be antennal specific but present in sensilla of both male and female antennae. MsexAOX was observed as a dimer with a combined estimated molecular mass of 295 kDa. M. sexta uses a multicomponent pheromone consisting exclusively of aldehydes including bombykal (Starratt el al., 1979 Tumlinson el al., 1989, 1994) MsexAOX was shown to degrade bombykal to its carboxylic acid. Both TLC and spectrophotometric assays were established and a variety of substrates and inhibitors were characterized. Making adjustments for the concentrations and volumes within a sensillum lumen, the in vivo half-life of pheromone was estimated at 0.6 msec in the presence of this enzyme (Rybczynski el al., 1989). 

Asymmetric hydrosilylation of 1,3-dienes provides convenient access to optically active a-chiral allylsilanes.107 1073 1071 The combination of 7r-allylpalladium chloride dimer with axially chiral monophosphine ligand 17 realizes high catalytic activity and enantioselectivity in the reaction of cyclic 1,3-dienes with HSiCl3.108,108a The allyltrichlorosilanes obtained react with aldehydes in a syn-Se mode to give homoallyl alcohols with high diastereo-and enantioselectivity (Scheme 9). 

Aldehyde C-H bonds can also undergo cyclometalation with palladium salts. Reaction of 8-quinolinecarbaldehyde with PdCLt gives a chloride-bridged dimer with a palladium-acyl bond (equation 75). No intermediates could be isolated in case of the palladium reaction, but when [(PEt3)PtCl2]2 is reacted with 8-quinolinecarbaldehyde, a platinum complex is isolated with an intact aldehyde C-H bond. The nitrogen atom of the quinoline is coordinated to the platinum, and the aldehyde C-H bond occupies an axial site in the complex. Heating this material results in insertion into the aldehyde C-H bond and formation of a chelated platinmn acyl. 

Polyacetylene aldehydes undergo a curious dimerization with loss of carbon monoxide " - . The reaction occurs spontaneously when concentrated solutions of the aldehydes 230 are allowed to stand at room temperature giving both Z and E isomers of the dimeric aldehydes 231. p-Substituted 5-phenyl-2,4-pcntadiynals (232)... 

One major advantage offered by the dppf ligand in Rh-catalyzed olefin hydroformylation is exemplified in its higher linear aldehyde selectivity when present in a dppf Rh ratio of 1.5 or higher [37,242]. This result leads to the proposed key intermediate of a Rh dimer with both chelating and bridging phosphine in the catalytic cycle. It also confirms the significance of the tris (phosphine) moieties at the point when the aldehyde selectivity is determined, i.e., the step in which the hydride is inserted into the M-olefin bond. This involvement of a dinuclear or tris (phosphine) intermediate appears to differ from the intermediate RhH(CO)(PR 3)z (olefin) (which is converted into the square planar Rh(R)(CO)(PR 3)2 by hydride insertion) commonly accepted for hydroformylation catalyzed by monophosphine complexes. P NMR studies also established the existence of the equilibrium in which the disphosphine can be... 

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