Photolysis of the thiohydroximate ester derivative 21 of 2-carboethoxy-2-(2-(benzylseleno)pyridin-3-yl)tridecylcarboxylic acid (20) affords 2-dodecyl-2-carboethoxy-2,3-dihydroselenolo[2,3-b]pyridine (22) in 89% yield in a process presumably involving intramolecular homolytic substitution by a tertiary alkyl radical at selenium with loss of a benzyl radical. Alternatively, rearrangement of O-(om...

The first general method for the reductive dimerization of alkyl halides, alkyl mesylates, alkyl trifluoroacetates, and allylic acetates is reported which proceeds with low catalyst loading (0.5 to 5 mol%), generally high yields (80% ave yield), and good functional-group tolerance.

This paper describes the selective reductions with thioborane derivatives, zinc—modified cyanoborohydride, and the ate complex from diisobutylaluminum hydride and n-butyllithium. Reaction of carboxylic acids with 1,3,2-dithiaborinane in the presence of stannous chloride or boron trifluoride etherate in tetrahydrofuran gives 1,3-dithianes in high yields. The reaction of acids with thexylphenylth...

A wide array of cross-coupling methods for the formation of C-C bonds from unactivated alkyl electrophiles have been described in recent years. In contrast, progress in the development of methods for the construction of C-heteroatom bonds has lagged; for example, there have been no reports of metal-catalyzed cross-couplings of unactivated secondary or tertiary alkyl halides with silicon nucleop...

A new route to α-alkyl-α-fluoromethylenebisphosphonates, 2 has been developed starting from commercially available tetraethyl fluoromethylenebisphosphonate (1), and alkyl halides using either caesium carbonate in DMF or sodium dimsyl. De-esterification of 2 provided biologically important α-alkyl-α-fluoromethylenebisphosphonic acid, 3, while alkoxide-induced carbon-phosphorus bond cleavage of 2...

An iron-catalyzed diboration reaction of alkynes with bis(pinacolato)diboron (B2pin2) and external borating agents (MeOB(OR)2) affords diverse symmetrical or unsymmetrical cis-1,2-diborylalkenes. The simple protocol for the diboration reaction can be extended to the iron-catalyzed carboboration of alkynes with primary and, unprecedentedly, secondary alkyl halides, affording various tetrasubstit...

A series of novel 2-alkylidene imidazolines has been synthesized from imidazolium halides and substituted alkyl halides in the presence of base. The resultant exocyclic enediamines have been characterized and their nucleophilicity has been evaluated upon NMR spectroscopic data and substitution reactions.

Selective catalytic synthesis of Z-olefins has been challenging. Here we describe a method to produce 1,2-disubstituted olefins in high Z selectivity via reductive cross-coupling of alkyl halides with terminal arylalkynes. The method employs inexpensive and nontoxic catalyst (iron(II) bromide) and reductant (zinc). The substrate scope encompasses primary, secondary, and tertiary alkyl halides, ...

Presented are the results of a systematic investigation of the reactions of nine-atom deltahedral clusters of germanium (Zintl ions, Ge(9)(n-)) with alkynes and alkyl halides that result in alkenylation and alkylation of the clusters, respectively. The reaction pathways have been probed in depth using various, appropriately substituted alkynes and organic halides, including some typical mechani...

The nickel-catalyzed cross-coupling of aryl halides with alkyl radicals derived from alkyl halides has recently been extended to couplings with carbon radicals generated by a co-catalyst. In this study, a new co-catalyst, cobalt phthalocyanine (Co(Pc)), is introduced and demonstrated to be effective for coupling substrates not prone to homolysis. This is because Co(Pc) reacts with electrophiles...