Catalysts working in tandem

Biocatalysts (of chemo/bio-catalysts working in tandem) able to fully convert the carbohydrates into ethanol and other fuels, and be robust and tolerant of the toxic compounds formed during the pretreatment (hydrolysis) process. 

Kinetic studies revealed that the polymerization by Cp 2Sm(THF)2 is zero-order in [yMMBL] and second-order in [catalyst], as a result of two samarium centers working in tandem to produce one polymer chain. This result, coupled with the polymerization initiator efficiency result, which also pointed to the bimetallic nature of the propagation, conforms to the proposed MMA polymerization mechanism by the same divalent catalyst involving a redox-then-radical-coupling initiation process, with the true active species being the two trivalent samarocene centers attached to the single growing polymer chain. 

Cyclic alkyl nitronates may be used in tandem [4+2]/[3+2] cycloadditions of nitroalkanes, and this reaction has been extensively studied by Denmark et al. (64,333-335). In recent work, they developed the silicon-tethered heterodiene-alkene 219 (Scheme 12.63). Steric hindrance and the fact that both the nitroalkene and the a,p-unsaturated ester in 219 are electron deficient renders the possibility of self-condensation. Instead, 219 reacts with the electron-rich chiral vinyl ether 220 in the presence of the catalyst 224 to form the intermediate chiral nitronate 221. The tandem reaction proceeds from 221 with an intramolecular 1,3-dipolar cycloaddition to form 222 with 93% de. Further synthetic steps led to the formation of ( )-detoxinine 223 (333). A similar type of tandem reaction has also been applied by Chattopadhyaya and co-workers (336), using 2, 3 -dideoxy-3 -nitro-2, 3 -didehydrothymidine as the starting material (336). 

Comprehensive EXAFS reviews on catalysis have been recently published. These encompass studies concerning surface mediated electrochemical processes and catalytic solids under environmental conditions. The first set of studies examined the local structural changes in the metal occurring in tandem with redox processes under voltage control. " Recent work in this area examines the stability of bimetallic Pt-Ru electrodes and their performance in the hydrogen oxidation reaction in the presence of CO or direct methanol fuel cells. Studies reviewed involving supported metal catalysts concern, in the first place, the reduction process " while other studies also consider the oxidation process and reduction under inert gases. All of these studies make an attempt to understand the relevance of the metal support interface... 

Continuing the investigation of tandem Ru-catalyzed reactions, Marc L. Snapper of Boston College effected Organic Lett. 2007, 9, 1749) metathesis with methacrolein 8a, then added Ph P and diazoacetate, to give the diene 11. A range of common Ru catalysts worked well for this transformation. In an alternative approach to trisubstituted alkene... 

Enantioselective Michael addition catalyzed by chiral aluminum Lewis acid is one of the most important methods to obtain enantiomerically pure compounds. As an early work in this fleld, in 1986, Shibasaki and coworkers reported catalytic enantioselective Michael addition of malonates to cyclic enones catalyzed by Li-Al bimetallic catalyst (72) (ALB) derived by premixing LiAlH4 and 2 equivalent of (R)-BINOL in THF (Scheme 6.86) [106, 107]. The structure of (R)-ALB was confirmed by X-ray crystallographic analysis of ALB-cyclohexenone complex. One notable advantage of ALB catalyst is that it works nicely in the tandem Michael-aldol sequence. 

A nickel hydride complex, NiHCl(diphenylphosphinoethane), catalyses the tandem isomerization-aldolization reaction of allylic alcohols with aldehydes.156 The atom- (g) efficient process proceeds at or below ambient temperature with low catalyst loading, and works well even for bulky aldehydes. Magnesium bromide acts as a co-catalyst, and mechanistic investigations suggest that a free enol is formed, which then adds to the aldehyde in a hydroxyl-carbonyl-ene -type reaction. 

Me3SiCN is a convenient, reactive cyanide donor in transition metal-catalyzed processes. The Pd-catalyzed reaction of aryl iodides with Me3SiCN is useful for the synthesis of aryl cyanides.257 Me3SiCN works also as an effective co-catalyst for the Pd-catalyzed cyanation of aryl iodides with KCN.258 Allylic acetates, carbonates, and the related compounds undergo the Pd-catalyzed cyanation with Me3SiCN.259-261 The tandem cyclization-cyanation reaction of 2-bromo-l,6-heptadienes with Me3SiCN proceeds under catalysis by an Ni complex (Equation (68)).262... 

Over the last twenty years, the tandem process involving transition metal-promoted cyclization reactions initiated or determined by a Michael addition has attracted an increasing interest in organic chemistry. The diversity of examples discussed in this work demonstrates the high potential of these tandem reactions for the efficient one-pot synthesis of complex structures with limiting catalysts and remarkable atom economy. It is expected that the development of further useful new sequences founded on this concept will be developed in the near future. 

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