Syntheses of (1R,2S,3R,4S)-1,7,7-trimethyl-2-pyridin-2-ylmethylbicyclo[2.2.1]-heptane-2,3-diol (7), (1R,2S,3R,4S)-1,7,7-trimethyl-2-[(6-methyl)-pyridin-2-ylmethyl-bicyclo-[2.2.1]heptane-2,3-diol (13), and (1R,2S,2’R,...Syntheses of (1R,2S,3R,4S)-1,7,7-trimethyl-2-pyridin-2-ylmethylbicyclo[2.2.1]-heptane-2,3-diol (7), (1R,2S,3R,4S)-1,7,7-trimethyl-2-[(6-methyl)-pyridin-2-ylmethyl-bicyclo-[2.2.1]heptane-2,3-diol (13), and (1R,2S,2’R,4R)-1,7,7-trimethyl-2-piperidin-2-ylmethyl-bicyclo[2.2.1]heptan-2-ol (19b) from commercially available (d)-camphor (1) are described. Key steps of the syntheses involved substrate-controlled diastereoselective alkylation and platinum oxide-catalyzed hydrogenation reactions. These compounds, and other intermediate amino alcohols in their syntheses, were successfully utilized as ligands in enantioselective diethyl zinc (Et2Zn) addition to benzaldehyde with moderate enantioselectivity.展开更多
Southern rootworm (Diabrotica undecimpunctata howardi) affects several plants such as soybean, sorghum, wheat, cucumber, alfalfa, cucurbits and it is most damaging to corn and peanuts. The pheromone based “attract an...Southern rootworm (Diabrotica undecimpunctata howardi) affects several plants such as soybean, sorghum, wheat, cucumber, alfalfa, cucurbits and it is most damaging to corn and peanuts. The pheromone based “attract and kill” strategy is one of the powerful ways to control pest population. To address our key objective of the practical utility of the synthetic pheromone, we have developed a simple synthetic strategy to produce gram scale southern corn rootworm pheromone in nine simple steps starting from S-Citronellol. The present strategy takes advantage of the existing chiral center of commercially available S-Citronellol. To get the basic carbon skeleton of the pheromone, the main step in the synthetic strategy is coupling of aliphatic units through Wittig reaction. The phosphonium salt from a non-functionalized aliphatic bromide followed by Wittig reaction improved the overall yield in the multistep synthesis of this pheromone. The large-scale production of pheromone enabled us to test it in the field.展开更多
文摘Syntheses of (1R,2S,3R,4S)-1,7,7-trimethyl-2-pyridin-2-ylmethylbicyclo[2.2.1]-heptane-2,3-diol (7), (1R,2S,3R,4S)-1,7,7-trimethyl-2-[(6-methyl)-pyridin-2-ylmethyl-bicyclo-[2.2.1]heptane-2,3-diol (13), and (1R,2S,2’R,4R)-1,7,7-trimethyl-2-piperidin-2-ylmethyl-bicyclo[2.2.1]heptan-2-ol (19b) from commercially available (d)-camphor (1) are described. Key steps of the syntheses involved substrate-controlled diastereoselective alkylation and platinum oxide-catalyzed hydrogenation reactions. These compounds, and other intermediate amino alcohols in their syntheses, were successfully utilized as ligands in enantioselective diethyl zinc (Et2Zn) addition to benzaldehyde with moderate enantioselectivity.
文摘Southern rootworm (Diabrotica undecimpunctata howardi) affects several plants such as soybean, sorghum, wheat, cucumber, alfalfa, cucurbits and it is most damaging to corn and peanuts. The pheromone based “attract and kill” strategy is one of the powerful ways to control pest population. To address our key objective of the practical utility of the synthetic pheromone, we have developed a simple synthetic strategy to produce gram scale southern corn rootworm pheromone in nine simple steps starting from S-Citronellol. The present strategy takes advantage of the existing chiral center of commercially available S-Citronellol. To get the basic carbon skeleton of the pheromone, the main step in the synthetic strategy is coupling of aliphatic units through Wittig reaction. The phosphonium salt from a non-functionalized aliphatic bromide followed by Wittig reaction improved the overall yield in the multistep synthesis of this pheromone. The large-scale production of pheromone enabled us to test it in the field.
