The use of surface-bound alkyl and phenyl groups as synthetic vehicles in coupling reactions on oxygen-activated Au(111) is demonstrated by the formation of ethers via alkyl and phenyl iodides. Ethers are formed by successive additions of surface-bound alkyl groups to adsorbed atomic oxygen to form first the alkoxy and then the ether. The addition of the ethyl group to adsorbed oxygen on Au(111...

The ability of the terpyridine ligand to stabilize alkyl complexes of nickel has been central in obtaining a fundamental understanding of the key processes involved in alkyl-alkyl cross-coupling reactions. Here, mechanistic studies using isotopically labeled (TMEDA)NiMe(2) (TMEDA = N,N,N',N'-tetramethylethylenediamine) have shown that an important catalyst in alkyl-alkyl cross-coupling reaction...

The metabolism of platelet-activating factor (PAF, 1-O-alkyl-2-acetyl-sn-glycero-3-phosphocholine) and lyso-PAF (1-O-alkyl-2-lyso-sn-glycero-3-phosphocholine) was investigated in FRTL5 cells, a normal rat thyroid cell line. FRTL5 cells incorporated [3H]PAF and deacetylated this compound to the corresponding [3H]lyso-PAF which was not accumulated or secreted but converted mainly to alkyl-acyl-ph...

Many cell surface proteins in mammalian cells are anchored to the plasma membrane via glycosylphosphatidylinositol (GPI). The predominant form of mammalian GPI contains 1-alkyl-2-acyl phosphatidylinositol (PI), which is generated by lipid remodeling from diacyl PI. The conversion of diacyl PI to 1-alkyl-2-acyl PI occurs in the ER at the third intermediate in the GPI biosynthetic pathway. This l...

The present research was undertaken to determine the conformations of alkyl groups that are forced into small spaces. Unbranched alkyl groups assume fully extended conformations in the free space of solutions, because any bends in the structure create steric clashes between hydrogens along the chain. We synthesized a series of alkyl esters of a carboxylic acid attached to the inner surface of a...

The substitution of a siloxy group using thiosilanes smoothly occurred in the presence of InI₃ catalyst to yield the corresponding thioethers. InI₃ was a specifically effective catalyst in this reaction system, while other typical Lewis acids such as BF₃⋅OEt₂, AlCl₃, and TiCl4 were ineffective. Various silyl ethers such as primary alkyl, secondary alkyl, tertiary alkyl, allylic, benzylic, and p...

We have compared the ability of beta-glucosidases from cassava, Thai rosewood, and almond to synthesize alkyl glucosides by transglucosylating alkyl alcohols of chain length C(1)-C(8). Cassava linamarase shows greater ability to transfer glucose from p-nitrophenyl-beta-glucoside to secondary alcohol acceptors than other beta-glucosidases, and is unique in being able to synthesize C(4), C(5), an...

Self-assembled layers of alkyl chains grafted onto the surfaces of layered silicates, metal, and oxidic nanoparticles are utilized to control interactions with external media by tuning the packing density of the chains on the surface, head group functionality, and chain length. Characterization through experiment and simulation shows that the orientation of the alkyl layers and reversible phase...

Functional microdomains of glycolipids were designed by mixing neoglycolipids with partially fluorinated alkyl (F-alkyl) chains and matrix lipids with alkyl chains. Fluorescence images of the mixed lipid monolayers at the air-water interface demonstrated that it is possible to control both size and distribution of the microdomains by means of the strong demixing of alkyl and F-alkyl membrane an...

Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C-H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of ge...