Curtin-Hammett versus non-Curtin-Hammett frameworks is optimizing the enantioselective binolam/titanium(IV)-catalyzed cyanobenzoylation of aldehydes: Part 2

Extensive experimental and computational studies have been carried out on the enantioselective titanium(IV)-catalyzed cyanobenzoylation of aldehydes using 1:n Binolam:Ti(OiPr)4 mixtures as precatalysts, with the purpose of identifying the key mechanistic aspects governing enantioselectivity. HCN and isopropyl benzoate were detected in the reacting mixtures. This, as well as the reaction’s response to the presence of an exogenous base, and the failure to react in the presence of Binol:Ti(OiPr)4 mixtures, led us to propose not a direct cyanobenzoylation but an indirect process involving enantioselective hydrocyanation followed by O-benzoylation. Computational work provided positive evidence for the intervention of both indirect and direct cyanobenzoylation routes, the former being faster. However, the standard Curtin–Hammett-based optimization search ended with unsatisfactory results. Experimental and computational DFT studies (B3LYP/6-31G*) led us to conclude that: (1) the overall cyanobenzoylation of aldehydes catalyzed by 1:n Binolam:Ti(OiPr)4 mixtures involves an enantioselective hydrocyanation followed by an stereochemically inert O-benzoylation; (2) the initial complexes prevailing in a 1:1 Binolam:Ti(OiPr)4 mixture are the solvated mononuclear monomer 5·2(iPrOH) and solvated dinuclear dimer 9·2(iPrOH), whereas 9·2(iPrOH) is the major component in a 1:2 or higher 1:n mixture; (3) since the slowest step is that of benzoylation of ligated iPrOH which yields the actual catalysts 5–9, the catalytic system fits into a non-Curtin–Hammett framework, the final products deriving from a kinetic quench of the competing routes; and (4) accordingly, catalysis by 1:1 Binolam:Ti(OiPr)4 mixtures should involve cyanobenzoylations promoted by mononuclear 5, contaminated with those promoted by some dinuclear open dimer 9, whereas cyanobenzoylations catalyzed by a 1:2 and higher 1:n mixtures should be the result of catalysis promoted by the large amounts of dinuclear open dimer 9.

When Spanish owns English words

The English language and the Internet, both separately and taken together, are nowadays well-acknowledged as powerful forces which influence and affect the lexico-grammatical characteristics of other languages world-wide. In fact, many authors like Crystal (2004) have pointed out the emergence of the so-called Netspeak, that is, the language used in the Net or World Wide Web; as Crystal himself (2004: 19) puts it, ‘a type of language displaying features that are unique to the Internet […] arising out of its character as a medium which is electronic, global and interactive’. This ‘language’, however, may be differently understood: either as an adaptation of the English language proper to internet requirements and purposes, or as a new and rapidly-changing and developing language as a result of a rapid evolution or adaptation to Internet requirements of almost all world languages, for whom English is a trendsetter. If the second and probably most plausible interpretation is adopted, there are three salient features of ‘Netspeak’: (a) the rapid expansion of all its new linguistic developments thanks to the Internet itself, which may lead to the generalization and widespread acceptance of new words, coinages, or meanings, hundreds of times faster than was the case with the printed media. As said above, (b) the visible influence of English, the most prevalent language on the Internet. Consequently, (c) this new language tends to reduce the ‘distance’ between English and other languages as well as the ignorance of the former by speakers of other languages, since the ‘Netspeak’ version of the latter adopts grammatical, syntactic and lexical features of English. Thus, linguistic differences may even disappear when code-switching and/or borrowing occurs, as whole fragments of English appear in other language contexts. As a consequence of the new situation, an ideal context appears for interlanguage or multilingual word formation to thrive: puns, blends, compounds and word creativity in general find in the web the ideal place to gain rapid acceptance world-wide, as a result of fashion, coincidence, or sheer merit of the new linguistic proposals.

Ferredoxin-dependent glutamate synthase: involvement in ammonium assimilation in Haloferax mediterranei

Glutamate synthase (GOGAT) is one of the two important enzymes involved in the ammonium assimilation pathway glutamine synthetase (GS)/GOGAT, which enables Hfx. mediterranei to thrive in media with low ammonium concentration or containing just nitrate as single nitrogen source. The gene coding for this enzyme, gltS, has been sequenced, analysed and compared with other GOGATs from different organisms from the three domains of life. According to its amino acid sequence, Hfx. mediterranei GOGAT displays high homology with those from other archaeal halophilic organisms and with the bacterial alpha-like subunit. Hfx. mediterranei GOGAT and GS expression was induced under conditions of ammonium restriction. The GOGAT protein was found to be a monomer with a molecular mass of 163.78 kDa, which is consistent with that estimated by gel filtration, 198 ± 30 kDa. The enzyme is highly ferredoxin dependent: activity was only observed with one of the two different 2Fe–2S ferredoxins chromatographically isolated from Hfx. mediterranei. The enzyme also displayed typical halophilic behaviour, being fully stable, and producing maximal activity, at salt concentrations from 3 to 4 M NaCl, pH 7.5 and a temperature of 50 °C.