Molybdenum-based complexes with two aryloxides and a pentafluoroimido ligand: catalysts for efficient Z-selective synthesis of a macrocyclic trisubstituted alkene by ring-closing metathesis.
Molybdenum-based complexes with two aryloxides and a pentafluoroimido ligand: catalysts for efficient Z-selective synthesis of a macrocyclic trisubstituted alkene by ring-closing metathesis.
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DOI：
10.1002/anie.201209180
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发表时间：
2013-02-11
影响因子：
16.6
通讯作者：
Hoveyda, Amir H.
中科院分区：
文献类型：
--
作者：
Wang, Chenbo;Haeffner, Fredrik;Schrock, Richard R.;Hoveyda, Amir H.
大环闭环复分解（RCM）对有机化学产生了巨大影响；[i，ii]尽管缺乏可靠的立体选择性催化剂控制方案，但这种影响仍然存在。高立体选择性对于复杂分子合成中的应用至关重要：非歧视性 RCM 通常在多步骤路线的后期进行，成本可能很高（总体产量降低≥ 50%）。我们已经报道，使用基于Mo或W的单芳氧基吡咯烷(MAP)络合物，可以有效地、立体选择性地获得大环二取代Z烯烃。[iii]另一个更具挑战性和战略上独特的问题涉及大环三取代烯烃的合成；[ii]在这种情况下，通过二炔RCM[iv]/炔官能化重新路由并不是一个有吸引力的选择。迄今为止，在大多数产生的催化RCM反应中观察到很少或根本没有立体选择性。 [v] 在存在立体化学控制的情况下，生成的形式可能是优选的形式 [vi]，或者通常是不需要的形式，[vii] 取决于可能的异构体之间的能量差异（底物控制）。在设计立体选择性地递送三取代大环烯烃的烯烃复分解催化剂时，需要克服许多挑战。首先，催化剂必须有效且立体选择性地促进烯烃形成，同时避免伴随反应较慢的烯烃的反应而发生的意外异构化
Macrocyclic ring-closing metathesis (RCM) has had an enormous impact on organic chemistry;[i, ii] such influence has been in spite of the absence of reliable stereoselective catalyst-controlled protocols. High stereoselectivity is crucial to applications in complex molecule synthesis: a non-discriminating RCM, often performed late stage in a multi-step route, can be costly (overall yield reduction by≥ 50%). We have reported that with Mo-or W-based mono-aryloxide pyrrolide (MAP) complexes, macrocyclic disubstituted Z olefins can be obtained efficiently and stereoselectively.[iii] Another problem, more challenging and strategically distinct, relates to synthesis of macrocyclic trisubstituted alkenes;[ii] re-routing through diyne RCM [iv]/alkyne functionalization is not an attractive option in such instances.Little or no stereoselectivity has hitherto been observed in most catalytic RCM reactions that produce a trisubstituted olefin within a large ring.[v] On occasions when there is stereochemical control, what is generated might be the preferred form [vi] or, frequently, one that is undesired,[vii] depending on the energy differential between the possible isomers (substrate-control). There are numerous challenges to be overcome in designing an olefin metathesis catalyst that stereoselectively delivers trisubstituted macrocyclic alkenes. First, the catalyst must efficiently and stereoselectively promote olefin formation, while avoiding adventitious isomerization that can accompany reactions of slower reacting alkene
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影响因子：
5.2
作者：
Hoye, TR;Zhao, HY
通讯作者：
Zhao, HY
影响因子：
2
作者：
Gaich, Tanja;Weinstabl, Harald;Mulzer, Johann
通讯作者：
Mulzer, Johann
DOI：
10.1002/anie.199615671
发表时间：
1996-07-26
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH
影响因子：
--
作者：
Hofle, GH;Bedorf, N;Reichenbach, H
通讯作者：
Reichenbach, H
影响因子：
15
作者：
Park, PK;O'Malley, SJ;Leighton, JL
通讯作者：
Leighton, JL
影响因子：
3.2
作者：
Michalak, Michal;Wicha, Jerzy
通讯作者：
Wicha, Jerzy