Department of Chemistry and Biochemistry , University of California , Santa Barbara , California 93106 , United States.
J Org Chem. 2019 Sep 6;84(17):11054-11060. doi: 10.1021/acs.joc.9b01613. Epub 2019 Aug 19.
An asymmetric total synthesis of diplobifuranylone B was achieved in 10 steps for the longest linear sequence and in 15.8% overall yield from commercially available methyl ()-(+)-lactate and l-glutamic acid. This synthesis features a stereoselective construction of the key 2,5-dihydrofuran ring in the natural product via a recently developed asymmetric gold catalysis. The stereochemical flexibility offered by the catalysis enables an expedient revision of the reported structure of diplobifuranylone B, where the relative stereochemistry of the 2,5-dihydrofuran moiety was previously misassigned as cis instead of trans.
从商业可得的（）-（+）-乳酸甲酯和 L-谷氨酸出发，经 10 步最长线性步骤和 15.8%总收率，实现了二倍双呋喃酮 B 的非对映选择性全合成。此合成通过最近开发的不对称金催化，立体选择性地构建天然产物中的关键 2,5-二氢呋喃环。该催化提供的立体化学灵活性使我们能够方便地修正二倍双呋喃酮 B 的报告结构，其中 2,5-二氢呋喃部分的相对立体化学以前被错误指定为顺式而不是反式。
