高度Z-选择性和enantioselective环开放/交叉转移被一个已解决的立体-at-Ru复合物催化
John Hartung1, Robert H Grubbs
1Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, United States.
Journal of the American Chemical Society
|July 5, 2013
概括
研究人员开发了一种新型的催化剂,用于Z选择性非对称环开放/交叉转移反应. 这种催化剂实现了高的Z选择性 (高达98%) 和反选择性 (高达95%).
科学领域:
- 有机金属化学 有机金属化学
- 不对称的催化剂.
- 有机合成 有机合成
背景情况:
- 不对称的环开放/交叉转移是有机合成中的一个关键转变.
- 开发具有高度选择性和enantioselective催化剂仍然是一个重大挑战.
- 基于的催化剂已被广泛探索为olefin转化反应.
研究的目的:
- 合成一种新型的复合物,用于不对称的环开放/交叉转移.
- 在催化过程中实现高Z选择性和选择性.
- 通过奇拉分辨率展示一种用于催化剂制备的新方法.
主要方法:
- 一个含有化N-异环碳联体的鲁丁复合物的合成.
- 使用奇拉性碳酸盐的N-异环碳酸复合物的分离.
- 在不对称的环开放/交叉转移反应中,合成的鲁丁复合物的应用.
主要成果:
- 合成的鲁复合物有效地催化了Z-选择性的不对称环开放/交叉转移.
- 在反应中达到高达98%的Z-选择性.
- 证明了高的反反选择性,达到高达95%的反反体过量 (ee).
结论:
- 成功合成了一种新型的催化剂,可实现高度Z选择性和酶选择性非对称环开放/交叉转移.
- 用性碳酸盐替代联体是一种有效的策略,用于解决化N-异环碳酸盐复合物的化.
- 这种催化剂代表了对不对称的烯转化物的重大进步.
相关概念视频
Base-Catalyzed Ring-Opening of Epoxides
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
Acid-Catalyzed Ring-Opening of Epoxides
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
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In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
E1 Reaction: Stereochemistry and Regiochemistry
One of the critical aspects of the E1 reaction mechanism, as also observed in E2, is the regiochemistry, with multiple regioisomers obtained as products. In the example discussed, the presence of water as a weak base favors elimination over substitution to generate two alkenes. Given that alkenes’ stability increases with the number of alkyl groups across the double bond, typically, E1 reactions lead to the Zaitsev product, for this is more substituted and stable than the Hofmann product.
Thermal Electrocyclic Reactions: Stereochemistry
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.

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