Efficient synthesis of substituted derivatives of (naphthalene)chromium(0) carbonyls
摘要:
Tricarbonyl(eta-6-1,4-epoxy-1,2,3,4-tetrahydronaphthalene) complex is a source of "protected" naphthalene for the indirect synthesis of Cr(eta-6-naphthalene)(CO)2L complexes, which can then be used in arene-exchange experiments. Experiments are reported for when L is a chiral 1,3,2-dioxaphospholane made by condensation of a chiral diol and PPhCl2. Direct photolysis reactions of these ligands with Cr(eta-6-naphthalene)(CO)3 gives the substituted complexes in very poor yield (< 3%). In contrast, photolysis reactions with the 1,4-epoxy-1,2,3,4-tetrahydronaphthalene complexes proceed in good (ca. 60-65%) yields, and subsequent dehydration by HBF4 and BF3 (ca. 50-65% yields) gives the substituted naphthalene complexes in an overall yield of 30-40% from the tricarbonyl. It is possible to exchange the naphthalene with monoarenes, though poor selectivity is observed in ligand-exchange experiments of the chiral naphthalene complexes with prochiral arenes.