| Description |
vi, 41 leaves : illustrations ; 29 cm |
| Summary |
"Partial rate data, asymmetric induction studies, interrupted experiments and additives studies indicate that copper(I) salt-phosphite complexes are destroyed during the course of reactions with dimethyl diazomalonate (1) and ethyl diazoacetate (2). All evidence is consistent with the copper(I) being oxidized to copper(II) and copper(0) being oxidized by impurities in the olefin which most probably are hydroperoxides. Several new copper(I) salt-phosphite complexes were prepared and examined but none proved as effective for decomposing (1) as copper(II) bis acetylacetonate. The utility of the copper (I) chloride-trimethyl phosphite complex for decomposing (1) is a function of the means of preparation. The three general methods employed furnished samples having superposable i.r. spectra and superposable proton nmr spectra but exhibited varying degrees of line broadening in the P³¹ nmr. The chiral mixed phosphite ligand 2-phenoxy-5,10,10-trimethyl-1,3-dioxa-2 phosphatricyclo[5,2,1[superscript 5,8],0[superscript 4,9]] decane (3) derived from 2,3 bornadiol failed to induce any asymmetric induction in the reaction between (2) and styrene when complexed with copper(I) iodide even though the ligand is chiral at four carbons and phosphorous"--Abstract, leaf iii. |
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