本論文主要是改善傳統合成α-C17-ethynyl-containing steroid衍生物(例如 mestranol及levonorgestrel)，因為使用乙炔氣體，可能產生爆炸性的危害。我們成功發展以一鍋化方式進行ethynylation，並開發出催化性的 desilylation reaction，可更簡便合成出ethynyl-containing steroid化合物(例如mestranol和levonorgestrel)。本研究過程，我們先將類固醇的C-17的位置，順利銜接上α-C17-trimethylsilylacetylenyl，在同一鍋反應中再加入0.05催化量的Tetrabutylammonium fluoride (TBAF)，可成功引入α-C17-ethynyl group。
另一方面延續本實驗室C21-substituted steroid化合物研究，我們實驗室成功發展出以hexamethylenetetramine 試劑將C21-bromo-3α-hydroxyl-
3β-methoxymethyl-5α-pregnan-20-one轉換成C21-amino-3α-hydroxyl-
3β-methoxymethyl-5α-pregnan-20-one。
A one-pot ethynylation and catalytic desilylation reaction was developed for the synthesis of α-C17-ethynyl-containing steroid derivatives (e.g. mestranol and levonorgestrel). Addition of trimethylsilylacetylide to the carbonyl group at C-17 of the steroids yielded the C-17α- trimethylsilylacetylenyl adducts, which was desilylated with a catalytic amount of TBAF (0.050 equiv) in one-pot.
On the other hand, our laboratory were successfully developed the new amination methodology to convert C21-bromo-3α-hydroxyl- 3β-methoxymethyl-5α-pregnan-20-one to C21-amino-3α-hydroxyl- 3β-methoxymethyl-5α-pregnan-20-one steroidal derivatives. The C21-amino- 3α-hydroxyl-3β-methoxymethyl-5α-pregnan-20-one can be used as the precursor for synthesis of C21- substituted steroid derivatives.
