Australian Research Council Centre of Excellence for Free Radical Chemistry and Biotechnology, Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
Org Lett. 2012 Nov 16;14(22):5652-5. doi: 10.1021/ol302619r. Epub 2012 Oct 30.
The first heteroatom-based dienophile cycloadditions to cross-conjugated alkenes ([n]dendralenes) are reported. Nitroso-dienophiles undergo smooth single and double Diels-Alder additions to the parent dendralenes with orientational regio- and stereoselectivity and, notably, with reactivity that depends upon the parity of the [n]dendralene. The first crystal structure of a cross-conjugated hexaene is reported. Vasella's nitroso-sugar reagent gives a highly enantiomerically enriched double cycloadduct with [3]dendralene. This bicyclic oxazine is successively dihydroxylated and then ring-opened to form a branched chain diamino tetrol.
首次报道了基于第一个杂原子的二烯亲环加成反应到交叉共轭烯烃([n]树枝状烯烃)。硝酮二烯亲环加成物以取向区域和立体选择性，以及显著地取决于[n]树枝状烯烃的奇偶性，对母体树枝状烯烃进行了平稳的单和双 Diels-Alder 加成。首次报道了一个交叉共轭六烯的晶体结构。Vasella 的硝酮糖试剂与[3]树枝状烯烃反应得到高对映体富集的双环加成物。这个双环恶嗪接着被二羟基化，然后开环形成支链二氨基四醇。
