Alkane functionalization

Ethers are named m substitutive lUPAC nomenclature as alkoxy derivatives of alkanes Functional class lUPAC names of ethers are derived by listing the two alkyl groups m the general structure ROR m alphabetical order as separate words and then adding the word ether at the end When both alkyl groups are the same the prefix di precedes the name of the alkyl group... 

Initial serendipity and long-term design leads to regioselective alkane functionalization. 

A mechanism has been proposed involving CO dissociation from the metal complex followed by oxidative addition of the diboron analog. This precedes the alkane functionalization process (Scheme 8). 

In the preceding discussion, we have covered recent discoveries which shed light on the first two steps of Pt(II) catalyzed alkane functionalization (Section III Scheme 4) alkane activation by Pt(II) and oxidation of the resulting platinum(II) alkyl. The final step is the release of the... 

In summary, the advances of the past few years have well demonstrated both the challenges and the promise of the Pt(II)/Pt(IV) redox couple for alkane functionalization. It should also be mentioned that the emerging conceptual understanding of the elementary steps involved in this process has also contributed to the development of methods to activate and functionalize alkyl groups in complex organic molecules. 

This mechanism is consistent with a number of observations. Kinetic studies on prolyl 4-hydroxylase [223] and thymine hydroxylase (EC 1.14.11.6) [224] suggest that cofactor binds first, followed by 02. The bound 02 appears to have superoxide character, as superoxide scavengers are competitive inhibitors of 02 consumption [225,226], It is also clear that the oxidative decarboxylation of the keto acid is a distinct phase of the mechanism from the alkane functionalization step, as these two phases can be uncoupled, particularly when poor substrate analogs are employed [227-229], Evidence for an Fe(IV) = 0 intermediate derives from studies with substrate analogs. Besides the hydroxylation of the 5-methyl group of thymine, thymine hydroxylase can also catalyze ally lie hydrox-ylations, epoxidation of olefins, oxidation of sulfides to sulfoxides, and N-de-... 

Methyl-branched alkanes function as an arrestant in the housefly pheromone (Adams and Holt, 1987 Nelson el al., 1981). They are abundant components of the insect cuticular lipids (Nelson and Blomquist, 1995) where they function in waterproofing (Gibbs, 1998) and serve in chemical communication (Blomquist et al., 1993, 1998). 

Alkane Functionalization with Homogenous Transition Metal Catalysts I 37... 

A versatile process for the syntheses of very long chain alkanes, functionalized derivatives, and some branched chain hydrocarbons../. Chem. Soc., Perkin Trans.,... 

Examples of alkane functionalization reactions of the type shown in equation (1) are first considered, in which the atom X to which the new C—X bond is form comes from metals in Group I, followed by subsequent groups in the Periodic Table. Within each section, radical, electrophilic and carbenoid mechanisms are (Uscussed. 

Alkane functionalization by electrophilic addition reactions is also possible for example, the particularly stable tertiary adamaniyl cation must be involved in equation (34), a reaction which gives an excellent 75% yield of adduct In a similar way, a variety of alkenes and arenes can be alkylated by alkanes, or alkanes acylated by RCOCl/AlBra. ... 

Shilov s catalytic process using a mixture of Pt(II) and Pt(IV) salts for the conversion of methane into methanol and methyl chloride in aqueous solution makes a chemical paradigm for alkane functionalization. One of the new approaches finds oxidative functionalization of methane is catalyzed by a (bipyrimidine)platinum(II) complex in concentrated sulfuric acid at 100 In... 

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