School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, United Kingdom.
J Am Chem Soc. 2011 Oct 26;133(42):16798-801. doi: 10.1021/ja207869f. Epub 2011 Sep 28.
A short (8 steps) synthesis of (+)-erogorgiaene in 44% overall yield from p-methylacetophenone is described. Key steps include lithiation/borylation-protodeboronation to build up the molecule and control the stereochemistry at C1 and C4. The C11 stereochemistry was similarly set up by using lithiation/borylation methodology. The use of a mixed, unhindered borane in the lithiation/borylation reaction proved critical to success in the reaction of the tetralone-derived carbamate to control the C4 stereochemistry. The power of the reagent controlled methodology is illustrated in the stereocontrolled synthesis of all of the diastereomers of (+)-erogorgiaene.
从对甲基苯乙酮出发，以 44%的总收率经 8 步反应简短地合成了 (+)-海兔烯。关键步骤包括锂化/硼化-脱保护反应构建分子并控制 C1 和 C4 的立体化学，C11 立体化学通过锂化/硼化方法来建立。在四氢吡喃酮衍生的氨基甲酸酯的锂化/硼化反应中使用混合非位阻硼烷被证明对控制 C4 立体化学的反应至关重要。试剂控制方法的威力在 (+)-海兔烯的所有非对映异构体的立体控制合成中得到了体现。
