Alkyne elementometalation-Pd-catalyzed cross-coupling. Toward synthesis of all conceivable types of acyclic alkenes in high yields, efficiently, selectively, economically, and safely: "green" way.
Alkyne elementometalation-Pd-catalyzed cross-coupling. Toward synthesis of all conceivable types of acyclic alkenes in high yields, efficiently, selectively, economically, and safely: "green" way.
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DOI：
10.1021/jo1003218
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发表时间：
2010-05-21
影响因子：
3.6
通讯作者：
Xu, Zhaoqing
中科院分区：
文献类型：
--
作者：
Negishi, Ei-ichi;Wang, Guangwei;Rao, Honghua;Xu, Zhaoqing
钯催化的交叉偶联反应，特别是涉及 Zn、Al、Zr（Negishi 偶联）和 B（Suzuki 偶联）的交叉偶联反应，共同给有机合成带来了“革命性”变化。因此，作为 R1M（M = Zn、Al、B、Cu、Zr 等）和 R2X（X = I、Br、OTs 等）生成的两个区域和立体定义的碳基团现在可以交叉偶联，得到基本上完全保留所有结构特征的 R1-R2。对于烯烃合成，炔元素金属化反应包括加氢金属化（B、Al、Zr 等）、碳金属化（Cu、Al-Zr 等）和卤硼化（BX3，其中 X 为 Cl、Br 和 I）已被证明至关重要。将重点讨论天然产物的高效和选择性（≥98％）合成含有所有可能类型的区域和立体定义的二取代和三取代烯烃的二烯、三烯和寡烯的一些代表性实例。一些有趣但不受欢迎的情况涉及烯基初始结构特性的丧失，这可归因于烯丙基钯物质的形成，必须抑制或避免这种情况。一些涉及 1,3-、1,4-和 1,5-二烯合成的例子也将被讨论。
Palladium-catalyzed cross-coupling reactions, especially those involving Zn, Al, Zr (Negishi coupling) and B (Suzuki coupling), collectively have brought about “revolutionary” changes in organic synthesis. Thus, two regio- and stereodefined carbon groups generated as R1M (M = Zn, Al, B, Cu, Zr, etc.) and R2X (X = I, Br, OTs, etc.) may now be cross-coupled to give R1–R2 with essentially full retention of all structural features. For alkene syntheses, alkyne elementometalation reactions including hydrometalation (B, Al, Zr, etc.), carbometalation (Cu, Al–Zr, etc.), and haloboration (BX3 where X is Cl, Br, and I) have proven to be critically important. Some representative examples of highly efficient and selective (≥98%) syntheses of di-, tri- and oligoenes containing regio- and stereodefined di- and trisubstituted alkenes of all conceivable types will be discussed with emphasis on those of natural products. Some interesting but undesirable cases involving loss of the initial structural identities of the alkenyl groups are attributable to the formation of allylpalladium species, which must be either tamed or avoided. Some such examples involving the synthesis of 1,3-, 1,4-, and 1,5-dienes will also be discussed.
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影响因子：
15
作者：
ANDERSON, RJ;CORBIN, VL;SIDDALL, JB
通讯作者：
SIDDALL, JB
影响因子：
1.8
作者：
ANDO, K
通讯作者：
ANDO, K
影响因子：
15
作者：
CARR, DB;SCHWARTZ, J
通讯作者：
SCHWARTZ, J
影响因子：
2.3
作者：
AGRIOS, KA;SREBNIK, M
通讯作者：
SREBNIK, M
影响因子：
1.8
作者：
Anastasia, L;Xu, C;Negishi, E
通讯作者：
Negishi, E