Site- and enantioselective formation of allene-bearing tertiary or quaternary carbon stereogenic centers through NHC-Cu-catalyzed allylic substitution.
Site- and enantioselective formation of allene-bearing tertiary or quaternary carbon stereogenic centers through NHC-Cu-catalyzed allylic substitution.
复制标题
DOI：
10.1021/ja211269w
复制
发表时间：
2012-01-25
影响因子：
15
通讯作者：
Hoveyda, Amir H.
中科院分区：
文献类型：
--
作者：
Jung, Byunghyuck;Hoveyda, Amir H.
催化对映选择性烯丙基取代导致烯丙基的独占加成（<2%丙炔加成）和叔或季C-C键的形成。使用市售的烯基硼酸松醇酯（不需要制备反应性更强但稳定性较差的硼酸衍生物）。铜的手性双齿n -杂环卡宾配合物（NHC）具有独特的SN2 '加成方式生成手性产物的能力。含烯基产物收率高达95%，SN2选择性高达98%，对映体比（er）为99:1。位置选择性nhc - cu催化对映体富集的烯丙烯的硼氢化和转化为相应的β-乙烯基酮证明了实用性。
Catalytic enantioselective allylic substitutions that result in exclusive addition of an allenyl group (<2% propargyl addition) and formation of tertiary or quaternary C–C bonds are described. Commercially available allenylboronic acid pinacol ester is used (preparation of a more reactive but less stable boronate derivative not required). Reactions are promoted by 5.0–10 mol % of sulfonate-bearing chiral bidentate N-heterocyclic carbene (NHC) complexes of copper, which exhibit the unique ability to furnish chiral products arising from SN2′ mode of addition. The desired allenyl-containing products are generated in up to 95% yield, >98% SN2′ selectivity and 99:1 enantiomeric ratio (er). Site-selective NHC–Cu-catalyzed hydroboration of enantiomerically enriched allenes and conversion to the corresponding β-vinyl ketones demonstrates utility.
登录
查看更多内容
影响因子：
15
作者：
Gao F;McGrath KP;Lee Y;Hoveyda AH
通讯作者：
Hoveyda AH
影响因子：
16.6
作者：
Brown, M. Kevin;May, Tricia L.;Hoveyda, Amir H.
通讯作者：
Hoveyda, Amir H.
影响因子：
5.2
作者：
Fandrick, Daniel R.;Saha, Jaideep;Senanayake, Chris H.
通讯作者：
Senanayake, Chris H.
影响因子：
15
作者：
Murphy, KE;Hoveyda, AH
通讯作者：
Hoveyda, AH
影响因子：
4.9
作者：
Das, Jaya Prakash;Marek, Ilan
通讯作者：
Marek, Ilan