Part 1: Synthesis of 3,7 dimethyl-7-methoxyoctane-2-ol (Osyrol) from Citronellol utilizing the Wacker Process Part 2: Developing a methodology for C(sp3)-H Arylation on the β Position of a Carboxylic Acid using a Removable Directing Group
Date of Graduation
Master of Science in Chemistry
College of Arts and Sciences
The synthesis of 3,7-dimethyl-7-methoxyoctane-2-ol (Osyrol), an important sandalwood odorant, from 3,7-dimethylocta-1,6-diene (dihydromyrcene) was recently accomplished by two groups, both utilizing a two-step epoxide formation and ring opening approach. Here, the synthesis of Osyrol from 3,7-Dimethyloct-6-en-1-ol (citronellol) is accomplished in a novel six-step approach. The key steps in this synthesis is the Wacker Oxidation of a terminal double bond followed by sodium borohydride (NaBH4) reduction. Though most of the steps in this reaction scheme resulted in limited success, the key steps occurred with high yields.
In the second chapter, the effects of 2-aminophenyl-1H-pyrazole (2-APP) as a removable directing group for C(sp3)-H arylation was explored, as it has been successful in a multitude of C(sp2)-H activation methodologies. The best results were obtained when silver acetate (AgOAc) was employed as a promoter to the palladium II acetate (Pd(OAc)2)catalyst, and iodo-toluene as the aryl source. The reaction was heated to 130 °C in toluene in a sealed microwave vial. This produced the arylated product in high yields (~90%), when aryl iodide used had low steric hindrance and strong electron-donating groups.
Lo, Stephen, "Part 1: Synthesis of 3,7 dimethyl-7-methoxyoctane-2-ol (Osyrol) from Citronellol utilizing the Wacker Process Part 2: Developing a methodology for C(sp3)-H Arylation on the β Position of a Carboxylic Acid using a Removable Directing Group" (2018). Master's Theses. 1177.
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