We demonstrate here that even the most electron-poor olefins undergo Os0,-catalyzed oxidations. The reduced reactivity of chloroolefins relative to their fluorine counterparts is explained by a size effect; in all other respects the chloroolefins behave analog~usly.~~] The procedure is also applicable to strained fluoroolefins, for example norbornene derivatives.Our results cannot be rationalized with the frequently held conception of the mechanism of the osmylation as the electrophilic attack of osmium tetroxide on the olefin. The pyridine base effect discussed by Corey et al.
The lysC/asd gene cluster of Corynebacterium glutamicum ATCC 13032 was cloned and sequenced. The lysC locus coding for aspartokinase consists of two in-frame overlapping genes, lysC alpha encoding a protein of 421 amino acids (Mr 44,300) and lysC beta encoding a protein of 172 amino acids (Mr 18,600). The C. glutamicum aspartokinase was purified and found to contain two proteins of Mr 47,000 and Mr 18,000. A C. glutamicum mutant expressing a feedback-resistant aspartokinase was shown to be changed in a single base pair of the lysC beta gene, leading to an amino acid exchange in the beta-subunit of the aspartokinase. In addition, the identified mutation was found to be responsible for the enhanced expression of the asd gene located downstream of lysC.
Structure‐performance relationships in the propene polymerization behaviour of a number of silicon bridged bisindenyl zirconocenes show a rational pattern. Prognosis of the polymerization behaviour of different type structures, however, often fails, which is demonstrated by three examples of new zirconocenes. These include two bisindenyl complexes with two‐membered silicon bridges and one isospecific bridged fluorenyl cyclopentadienyl species. It is thus demonstrated that the scope of a “rational catalyst design” in the field of metallocene catalysts is still limited.
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