The D and L amino acid mediated enantioselective intramolecular aldol reaction of 4-((1-methyl-2,6-dioxo-cyclohexyl)methyl)-pent-4-enal 1 leading, after dehydration, to (-)-(R) and (+)-(S) 4a-methyl-3-methylene-5-oxo-2,3,4,4a,5,6,7,8-octahydro-naphthalene-1-carbaldehyde 2 was explored. It was found that (-)-(R) carbaldehyde 2 is enantioselectively formed in the presence of l-amino acids while (+)-(S) carbaldehyde 2 is enantioselectively formed in the presence of d-amino acids. (-)-(R) Carbaldehyde 2 was then transformed into (+)-22. The absolute configuration and relative stereochemistry of the latter was established by single-crystal X-ray diffraction analysis of p-iodobenzoate (+)-23.
Enantioselective Synthesis and X Ray determination of (+)((4aS,5S,8aS)-5,8a-dimethyl-7-methyleneoctahydro-2H-spiro [naphthalene-1,2'-[1,3]dioxolan]-5-yl)methyl-4-iodobenzoate
Lamba D;
2019
Abstract
The D and L amino acid mediated enantioselective intramolecular aldol reaction of 4-((1-methyl-2,6-dioxo-cyclohexyl)methyl)-pent-4-enal 1 leading, after dehydration, to (-)-(R) and (+)-(S) 4a-methyl-3-methylene-5-oxo-2,3,4,4a,5,6,7,8-octahydro-naphthalene-1-carbaldehyde 2 was explored. It was found that (-)-(R) carbaldehyde 2 is enantioselectively formed in the presence of l-amino acids while (+)-(S) carbaldehyde 2 is enantioselectively formed in the presence of d-amino acids. (-)-(R) Carbaldehyde 2 was then transformed into (+)-22. The absolute configuration and relative stereochemistry of the latter was established by single-crystal X-ray diffraction analysis of p-iodobenzoate (+)-23.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
