Substituent-Enhanced Intermolecular Catalytic Ene-yne Metathesis for Efficient 1,3-Diene Synthesis
Substituent-Enhanced Intermolecular Catalytic Ene-yne Metathesis for Efficient 1,3-Diene Synthesis
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取代基增强分子间催化烯-炔复分解用于高效合成 1,3-二烯
DOI：
10.1021/acscatal.1c04074
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发表时间：
2022
期刊：
影响因子：
12.9
通讯作者：
Sadow, Aaron D.
中科院分区：
文献类型：
--
作者：
Basemann, Kevin;Schmidt, Bradley M.;Sadow, Aaron D.
钌催化炔-炔复合反应的适宜条件受末端炔反应物上取代基和官能团的影响很大。我们已经确定了两种不同的方法，使用单一预催化剂IMes(Cl)2Ru(= CHC6H4OiPr) （1; IMes = 1,3-维咪唑-2-乙基），在无杂原子或功能化的末端炔和乙烯的乙烯-炔复分解反应中需要实现高转化率和高收率。在单一基准条件下，即3 mol %的1，甲苯，75°C和20 bar C2H4，一系列末端炔的烯-炔复合反应得到了广泛的1,3-二烯，确定了性能高，中等或较差的炔烃基团。研究反应条件对产率、周转率和这些基团的反应效率的影响，得出了有效合成的不同优化方法。在制备规模的实验中，在常规条件下，将高效炔和1混合，然后用乙烯加压，使用基准负载的五分之一，即0.6 mol %的1，获得了定量产率。相比之下，计量加成法，其中一个中等或较差性能的炔和溶液1缓慢和单独添加到乙烯加压反应容器，可以提高周转率高达1500%，以获得2-取代-1,3-二烯-含羧酸，羰基，胺，环氧化物，或卤化物在一个步骤。此外，稀释条件下功能化炔的有效反应速率增加，并与无杂原子炔的转化进行比较，表明前者在烯-炔的转化中比后者反应更快，但它们的转化对催化剂失活也更敏感。
The appropriate reaction conditions for ruthenium-catalyzed ene-yne metathesis are substantially affected by the substituents and functional groups on the terminal alkyne reactant. We have identified that two distinct methods, utilizing a single precatalyst IMes(Cl)2Ru(═CHC6H4OiPr) (1; IMes = 1,3-dimesitylimidazol-2-ylidene), are needed to achieve high turnovers and good yields in ene-yne metathesis reactions of heteroatom-free or functionalized terminal alkynes and ethylene. The wide-ranging yields of 1,3-dienes from ene-yne metathesis of a series of terminal alkynes under a single set of benchmark conditions, namely, 3 mol % of1, toluene, 75 °C, and 20 bar C2H4, identified groups of highly, moderately, or poorly performing alkynes. Studies of the effects of reaction conditions on yields, turnovers, and effective rates in the reactions of alkynes from these groups lead to distinct optimized approaches for efficacious syntheses. Quantitative yields are obtained using 0.6 mol % of1, one fifth of the benchmark loading, in preparative-scale experiments under conventional conditions in which the highly efficient alkyne and1are mixed, followed by pressurization with ethylene. In contrast, the metered addition method, in which a moderately or poorly performing alkyne and a solution of1are slowly and separately added to an ethylene-pressurized reaction vessel, can improve turnovers up to 1500% to access 2-substituted-1,3-diene-containing carboxylic acids, carbonyls, amines, epoxides, or halides in a single step. Moreover, the increased effective rates of reactions for functionalized alkynes under dilute conditions, and comparisons with heteroatom-free alkyne conversions, suggest that the former reacts more rapidly than the latter in ene-yne metathesis, but their transformations are also more sensitive to catalyst deactivation.
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DOI：
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发表时间：
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期刊：
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DOI：
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发表时间：
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