Total synthesis of the lipoxygenase substrates (5Z,8Z,11Z,14Z)-Nonadeca-5,8,11,14-tetraene-1,19-dioic acid and (5Z,8Z,11Z,14Z)-20,20-dimethylheneicosa-5,8,11,14-tetraenoic acid

摘要

For mechanistic studies on the lipoxygenase reaction, the special substrate fatty acids (5Z,8Z,11Z 14Z)-nonadeca-5,8,11,14-tetraene-1,19-dioic and (5Z,8Z,11Z,14Z)-20,20-dimethylheneicosa-5,8,11,4-tetraenoic acids were synthesized. The synthetic scheme involves a joint route for the formation of (5Z,8Z,11Z,14Z)-nonadeca-5,8,11,14-tetraene-1,19-dioic acid, which is based on the polyacetylenic approach. Regioselective reduction of the omega-carboxylic group to the primary alcohol, exchange of an OH-group to corresponding iodine and subsequent coupling with low-order organocuprates (t-Bu2CuLi) resulted in the formation of (5Z,8Z,11Z,14Z)-20,20-dimethylheneicosa-5,8, 11,14-tetraenoic acid with an overall yield of 11%. [References: 12]