Highly Stereoselective Cobalt(III)-Catalyzed Three-Component C-H Bond Addition Cascade.
Highly Stereoselective Cobalt(III)-Catalyzed Three-Component C-H Bond Addition Cascade.
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DOI：
10.1002/anie.201603831
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发表时间：
2016-10-04
期刊：
影响因子：
--
通讯作者：
Ellman JA
中科院分区：
文献类型：
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作者：
Boerth JA;Hummel JR;Ellman JA
报道了一个高立体选择性的三组分C（sp2）-H键加成反应，其中Co（III）催化剂比Rh（III）催化剂更有效。反应在环境温度下进行，芳基和烷基烯酮用作有效的偶联配偶体。此外，该反应表现出非常宽的范围，相对于醛输入与富电子和贫电子的芳族，烯基，支链和非支链的烷基醛，所有耦合在良好的产率和高非对映选择性。多个定向基团参与这种转化，包括吡唑、吡啶和亚胺官能团。芳族和烯基C（sp2）-H键都经历三组分加成级联，并且烯基加成产物可以容易地转化为非对映体纯的5元内酯。此外，第一个不对称反应与Co（III）催化的C-H官能化证明与三组分C-H键加成级联采用N-叔丁烷亚磺酰基亚胺。这些实施例代表第一过渡金属催化的C-H键加成到N-叔丁烷亚磺酰基亚胺，其已被证明是胺的不对称合成的通用和广泛使用的中间体。报道了一种高立体选择性的三组分C（sp2）-H键加成反应。Co（III）催化比Rh（III）更有效，提供良好产率的产物，并且对于非常宽范围的醛具有高的非对映选择性。此外，第一个不对称反应采用Co（III）催化的C-H官能化的三组分C-H键加成级联与N-叔丁基亚磺酰基亚胺的报告。
A highly stereoselective three-component C(sp2)–H bond addition across alkene and polarized π-bonds is reported for which Co(III) catalysis was shown to be much more effective than Rh(III). The reaction proceeds at ambient temperature with both aryl and alkyl enones employed as efficient coupling partners. Moreover, the reaction exhibits extremely broad scope with respect to the aldehyde input with electron rich and poor aromatic, alkenyl, and branched and unbranched alkyl aldehydes all coupling in good yield and with high diastereoselectivity. Multiple directing groups participate in this transformation, including pyrazole, pyridine, and imine functionalities. Both aromatic and alkenyl C(sp2)–H bonds undergo the three-component addition cascade, and the alkenyl addition product can readily be converted to diastereomerically pure 5-membered lactones. Additionally, the first asymmetric reactions with Co(III)-catalyzed C–H functionalization are demonstrated with three-component C–H bond addition cascades employing N-tert-butanesulfinyl imines. These examples represent the first transition metal catalyzed C–H bond additions to N-tert-butanesulfinyl imines, which have proven to be versatile and extensively used intermediates for the asymmetric synthesis of amines. A highly stereoselective three-component C(sp2)–H bond addition across alkene and polarized π-bonds is reported. Co(III) catalysis was much more effective than Rh(III) providing products in good yield and with high diastereoselectivity for an extremely broad range of aldehydes. Additionally, the first asymmetric reactions employing Co(III)-catalyzed C–H functionalization are reported for three-component C–H bond addition cascades with N-tert-butanesulfinyl imines.