Smith activation

M. F. Paugam, B. D. Smith, Active-transport of uridine through a liquid organic membrane mediated by phenylboronic acid and driven by a fluoride-ion gradient, Tetrahedron Letters 1993, 34, 3723. 

Simmons-Smith reagent Named after the duPont chemists who discovered that diiodo-mechane would react with an active zinc-copper couple in ether to give a reagent with molecular formula ICHiZnl. The reagent adds stereospecifically cis- to alkenes to give cyclopropanes in high yields. 

Nachtigaii P, Jordan K D, Smith A and Jdnsson H 1996 investigation of the reiiabiiity of density functionai methods reaction and activation energies for Si-Si bond cieavage and H2 eiimination from siianes J. Chem. Phys. 104 148... 

Carhart R E, D H Smith and R Venkataraghavan 1985. Atom Pairs as Molecular Features in Structure Activity Studies Definition and Applications. Journal of Chemical Information and Computer Scienc 25 64-73. 

Mills and Smith (504) were the first, in 1922, to develop a systematic study of the reactivity of methyl groups fixed on nitrogen-containing heterocycles. While in alkylpyridines the 2- (or 6) and 4-positions are activated, only the 2-position in thiazole corresponds to an enhanced reactivity of the methyl groups in condensation with aldehydes 4- and 5-methylthiazoles bear inert methyl groups. Quatemization of the thiazole nitrogen enhances still further the reactivity of the methyl in the 2-position (cf. Chapter IX), but it does not increase the reactivity of a methyl group in the 4-position (504). The authors invoke the possibility for 2- (and 6) methylpyridine and 2-methylthiazole to pass, to some extent, into the reactive enamine form (245), while 4-methylthiazole could adopt such a structure only with the participation of an unusual formula such as 247 (Scheme 112). 

Further evidence pointing in the same direction was provided by Pierce, Wiley and Smith, who found that on steam activation of a particular char at 900°C the saturation uptake increased three-fold, yet the isotherm was still of Type I. They argued that even if the width of the pores was only two molecular diameters before activation, it would increase, by removal of oxides, during the activation so that the second Type I isotherm would correspond to pores more than two molecular diameters wide. (The alternative explanation, that activation produced new pores of the same width as the old, seems unlikely.)... 

M. D. Smith, Decomposition ofHac rdous Organic Materials byRF. Activated Gas Plasma, AUiedSignal Inc., Kansas City, Mo., Mar. 1987, p. 

Helium [7440-59-7] M 4.0. Dried by passage through a column of Linde 5A molecular sieves and CaS04, then passed through an activated-charcoal trap cooled in liquid N2, to adsorb N2, argon, xenon and krypton. Passed over CuO pellets at 300° to remove hydrogen and hydrocarbons, over Ca chips at 600° to remove oxygen, and then over titanium chips at 700° to remove N2 [Arnold and Smith 7 Chem Soc, Faraday Trans 2 77 861 1981]. 

Reverse transcriptase (from avian or murine RNA tumour viruses) [9068-38-6] [EC 2.7.7.49]. Purified by solubilising the virus with non-ionic detergent. Lysed virions were adsorbed on DEAE-cellulose or DEAE-Sephadex columns and the enzyme eluted with a salt gradient, then chromatographed on a phosphocellulose column and enzyme activity eluted in a salt gradient. Purified from other viral proteins by affinity chromatography on a pyran-Sepharose column. [Verna Biochim Biophys Acta 473 1 7977 Smith Methods Enzymol 65 560 1980 see commercial catalogues for other transcriptases.]... 

A mixture of the epoxide ca. 5 mmol), sodium azide (6 g, activated by the method of Smith) and 0.25 ml of concentrated sulfuric acid in 70 ml of dimethyl sulfoxide is heated in a flask fitted with a reflux condenser and a drierite tube on a steam bath for 30-40 hr. (Caution carry out reaction in a hood.) The dark reaction mixture is poured into 500 ml of ice water and the product may be filtered, if solid, and washed well with water or extracted with ether and washed with sodium bicarbonate and the water. The crude azido alcohols are usually recrystallized from methanol. 

Studies by Smith et al. (1982), Folkard et al. (1979), and Colquhoim et al. (1969), have investigated the disruption of circadian rhythms caused by having to be awake and work at imusual hours and by having to sleep during daytime. With respect to the sociological effects, studies by Kasl (1974) and Kahn (1974) concluded that fixed afternoon and night shifts lead to lower levels of social satisfaction because it becomes difficult to participate in family activities. 

Smith et al determined the activation barrier for H2OETNP by NMR in CD2CI2 at 300 MHz (ZIGI73 = 55.2 kJ mor )(94JA3261) and found it to be similar to that measured for NH tautomerism in other free-base dodeca-substituted porphyrins (90JA8851, 92JA9859, 93IC1716). Finnish authors have reported a detailed study of the tautomerism of a natural chlorin. 

These initial reports demonstrated that a catalytic asymmetric variant of the Simmons-Smith reaction could be developed. Although good yields and selectivities were obtained, the lack of a clear understanding of the origin of activation, the limited structural information on the active species and the absence of a stereochemical model made rational improvements difficult at best. The next... 

This study suggests a radically new explanation for the nature of Lewis acid activation in the Simmons-Smith cyclopropanation. The five-centered migration of the halide ion from the chloromethylzinc group to zinc chloride as shown in TS2 and TS4 has never been considered in the discussion of a mechanism for this reaction. It remains to be seen if some experimental support can be found for this unconventional hypothesis. The small energy differences between all these competing transition states demand caution in declaring any concrete conclusions. 

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