Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.
Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.
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DOI：
10.1021/ja409995w
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发表时间：
2013-11-27
影响因子：
15
通讯作者：
Hartwig JF
中科院分区：
文献类型：
--
作者：
Sharma A;Hartwig JF
我们报告的烯丙基C-H键的末端烯烃的不对称选择性官能化的战略，包括安装一个临时官能团在末端碳原子的C-H键官能化，然后通过多样化的中间体与广泛的试剂。该方法包括一锅序列的钯催化的烯丙基C-H键氧化在中性条件下形成线性烯丙基苯甲酸酯，然后铱催化的烯丙基取代。该转化反应生成的手性产物在烯丙基位上含有新的C-N、C-O、C-S或C-C键，产率高，具有高的支链-直链选择性和优异的对映体选择性（ee ≤ 97%）。整个工艺的广泛范围来自于分离氧化和官能化步骤;通过这样做，亲核试剂的范围包括对直接氧化官能化敏感的那些。整个过程的高对映体选择性是通过开发在没有酸的情况下发生的烯丙基氧化以高选择性形成线性异构体来实现的。这些烯丙基官能化过程是服从于一个迭代序列，导致（1，n）-官能化的产品与催化剂控制的非对映体和对映体选择性。该方法在合成生物活性分子中的实用性已得到证实。
We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S or C-C bond at the allylic position in good yield with high branched-to-linear selectivity and excellent enantioselectivity (ee ≤ 97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.
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影响因子：
15
作者：
Campbell AN;White PB;Guzei IA;Stahl SS
通讯作者：
Stahl SS
影响因子：
62.1
作者：
Colby, Denise A.;Bergman, Robert G.;Ellman, Jonathan A.
通讯作者：
Ellman, Jonathan A.
通过ENE反应/[2,3] - 重新培训对未激活的末端烯烃的催化对映选择性烯丙基胺化。
影响因子：
15
作者：
Bao, Hongli;Tambar, Uttam K.
通讯作者：
Tambar, Uttam K.
影响因子：
1.8
作者：
El-Qisiari, AK;Qaseer, HA;Henry, PM
通讯作者：
Henry, PM
影响因子：
5.2
作者：
Gaunt, MJ;Jessiman, AS;Ley, SV
通讯作者：
Ley, SV