Enantioselective Intramolecular C–H Insertion Reactions of Donor–Donor Metal Carbenoids

The
first asymmetric insertion reactions of donor–donor
carbenoids, i.e., those with no pendant electron-withdrawing groups,
are reported. This process enables the synthesis of densely substituted
benzodihydrofurans with high levels of enantio- and diastereoselectivity.
Preliminary results show similar efficiency in the preparation of
indanes. This new method is used in the first enantioselective synthesis
of an oligoresveratrol natural product (E-δ-viniferin).

本研究首次报道了供体-供体卡宾类（donor–donor carbenoids）——即不含悬挂式吸电子基团的卡宾物种——的不对称插入反应。该反应可实现高对映选择性与非对映选择性的高度取代苯并二氢呋喃类化合物的合成。初步实验结果表明，该方法在茚满类化合物的制备中同样可达到相近的反应效率。此项全新合成方法首次被应用于低聚白藜芦醇天然产物E-δ-viniferin的对映选择性全合成。