Strategies and tactics in olefin metathesis

Kotha, Sambasivarao; Dipak, Mirtunjay Kumar

doi:10.1016/j.tet.2011.10.018

Cited by 136 publications

(60 citation statements)

References 232 publications

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“…7,8 Fischer carbenes are known to be electrophilic and are thus susceptible to nucleophilic attack on the carbene carbon. 4,7,9 Alkoxycarbenes are readily altered in this manner, which leads to the formation of amino, thio-and aryl-carbene complexes, respectively (reaction 3, Figure 1). 10 Of these modifications, aminolysis has been used most extensively 11 because of the relative ease of the reaction and the increased stability of the products.…”

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confidence: 99%

Synthesis, Structure, and Electrochemistry of Fischer Alkoxy- and Aminocarbene Complexes of Tungsten: The Use of DFT To Predict and Understand Oxidation and Reduction Potentials

et al. 2013

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Reactions of Fischer alkoxycarbene complexes[W(CO) 5 {C(OEt)Ar}], Ar = thienyl (1) or furyl (2), with ethylene diamine lead to the formation of two different reaction products: an aminolysis product (5 or 6) where the ethoxy substituent of the carbene ligand is replaced by the ethylene diamine moiety, as well as a chelated product where aminolysis and substitution of one carbonyl ligand had taken place, yielding 7 or 8. Aminolysis of 1 and 2 with cyclohexyl amine (CHA) produced the aminocarbene complexes 3 (Ar = thienyl) and 4 (Ar = furyl). Complexes 1-8 are electrochemically investigated by means of cyclic voltammetry. The relative shifts in the oxidation and reduction potentials are discussed and related to density functional theory (DFT) calculated energies. DFT calculations further show that the oxidation center is located on the metal and the carbonyl groups, while the reduction center is localized on the carbene moiety and is strongly influenced by the electronic properties of its substituents. Crystal structures of 1-4, 6 and 8 are reported.

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confidence: 99%

Synthesis, Structure, and Electrochemistry of Fischer Alkoxy- and Aminocarbene Complexes of Tungsten: The Use of DFT To Predict and Understand Oxidation and Reduction Potentials

et al. 2013

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“…HRMS (ESI, 13H),2H),2H),4H),4.65 (s,2H),2.42 (dd,2H,J ¼ 5.6 Hz,14.4 Hz),2.14 (dd,2H,J ¼ 8.5 Hz,14.6 Hz). 13 C NMR (CDCl 3 , 100 MHz): d ¼ 178. 5,140.0,139.4,133.7,131.6,129.1,128.8,127.1,126.8,126.7,126.5,125.3,119.4,55.7,51.6,37.3.…”

Section: Methodsmentioning

confidence: 99%

“…White solid (yields given in Table 2 7.45-7.37 (m, 2H), 7.34-7.29 (m, 2H), 7.28-7.24 (m, 4H), 7.24-7.17 (m, 4H), 6.50-6.37 (m, 2H), 5.84-5.72 (m, 2H), 2.94-2.78 (m, 2H), 1.83-1.71 (m, 2H). 13 C NMR (CDCl 3 , 100 MHz): d ¼ 180.0, 140. 5, 140.2, 129.1, 128.8, 127.9, 127.2, 127.1, 127.0, 126.7, 126.6, 125.2, 57.3, 51.5, 30 We have extended this methodology to the cage compound 42 to produce the basketene-based propellane derivative 45.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of propellanes containing a bicyclo[2.2.2]octene unitviathe Diels–Alder reaction and ring-closing metathesis as key steps

Kotha

Pulletikurti

2018

RSC Adv.

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The synthesis of propellanes containing bicyclo[2.2.2]octene via olefin metathesis approach is less explored.Herein, we describe a simple and convenient method to synthesize propellane derivatives containing a bicyclo[2.2.2]octene unit which are structurally similar to 11b-HSD1 inhibitors by sequential usage of the Diels-Alder reaction, C-allylation and ring-closing metathesis (RCM) as the key steps. Additionally, we expanded this approach to an endo-tricyclo[4.2.2.0 2,5 ]decene derivative which is a useful monomer for polymer synthesis and we have also synthesized basketene and anthracene-based propellanes using the same strategy.

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“…In light of the biological properties and applications of lactones obtained from synthetic routes involving OM reactions, it should also be mentioned that the removal of catalyst impurities from the organic product represents a challenging task. The initial and latest experimental strategies adopted for the separation of the ruthenium impurities have been described in recent review articles [240,241], whose contents can be particularly useful in the synthesis of natural products.…”

Section: Summary Conclusion and Outlookmentioning

confidence: 99%