Efficient Ring Closing Metathesis by NHC-Supported (Arylimido)vanadium(V)-Alkylidene Catalysts Containing Perhalophenoxide Ligands: Exclusive RCM under High Substrate Concentration

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-08-21 DOI:10.1021/acs.organomet.5c00224

Jirapa Suthala, Moe Unoki, Michael R. Buchmeiser* and Kotohiro Nomura*,

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引用次数: 0

Abstract

Ring closing metathesis (RCM) reactions of N,N-diallyl-4-toluenesulfonamide (S1) and N,N-diallylaniline (S2) by V(N-2,6-Cl₂C₆H₃)(CHSiMe₃)(OC₆X₅)(NHC) [X = F, Cl (4), Br (5); NHC = 1,3-bis(2,6-dimethylphenyl)imidazole-2-ylidene (IXy)] exclusively afforded the corresponding ring closed products (yields 83 to >99%) under high initial substrate concentration conditions (3.2–24 M). A significant increase in the activity was observed upon increasing the substrate concentrations, leading to highly efficient RCM [RCM of S2 by 4,5: TON = >1000, TOF = >100 s^–1, yield (conv.) 95 to >99%]. The RCM of diallyl ether and diallyl thioether afforded the corresponding ring closed products exclusively, whereas the activities increased with dilution of the substrate concentrations. The RCM of 1,7-octadiene also gave cyclohexene.

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含过卤代酚配体的nhc负载（芳基氨基）钒(V)-烷基基催化剂的高效合环复合反应：高底物浓度下的独占RCM

V(N-2,6- cl2c6h3)(CHSiMe3)(OC6X5)(NHC) [X = F, Cl (4), Br(5)]与N，N-二烯丙基-4-甲苯磺酰胺（S1）和N，N-二烯丙基苯胺（S2）的合环复合反应（RCM）NHC = 1,3-二（2,6-二甲基苯基）咪唑-2-酰基（IXy）]在高初始底物浓度条件下（3.2-24 M），只提供相应的环状封闭产物（产率83 - 99%）。随着底物浓度的增加，活性显著增加，导致高效率的RCM [S2的RCM增加4,5:TON = >1000, TOF = >100 s-1，收率（conv.） 95至>；99%]。二烯丙基醚和二烯丙基硫醚的RCM只产生相应的环封闭产物，而活性随着底物浓度的稀释而增加。1,7-辛二烯的RCM也得到环己烯。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.