<i>Z</i>-Selective Homodimerization of Terminal Olefins with a Ruthenium Metathesis Catalyst

Keitz, Benjamin K.; Endo, Koji; Herbert, Myles B.; Grubbs, Robert H.

doi:10.1021/ja203488e

Cited by 153 publications

(80 citation statements)

References 31 publications

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“…These "stereogenic-at-Mo" complexes were highly efficient in Z-selective cross metathesis as well as ring-closing metathesis for the stereoselective synthesis of antitumor agent KRN7000 [190] and the macrocyclic natural products epothilone C and nakadomarin A [191], respectively. Shortly thereafter, chiral N-heterocyclic carbene ruthenium complexes were reported as being Z-selective olefin metathesis catalysts [192][193][194][195][196]. Recently, the advances in the catalytic stereoselective olefin metathesis have been extensively reviewed by Hoveyda, and this overview is recommended to the reader for more information about this topic [197].…”

Section: Z-selective Rcm Of Peptidesmentioning

confidence: 99%

Synthesis of Cyclic Peptides and Peptidomimetics by Metathesis Reactions

Rijkers

2015

Topics in Heterocyclic Chemistry

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This review surveys developments in the field of ring-closing metathesis and cross-metathesis reactions applied to the synthesis of constrained amino acids, peptides, and peptidomimetics. Examples, in which metathesis is used as one of the synthetic tools to arrive at the desired peptide molecules as well as examples that describe in-depth optimized metathesis protocols, will be discussed. Currently, metathesis reactions are well-accepted synthetic tools within the field of peptide chemistry and provide peptides unprecedented properties like conformational, metabolic, and chemical stability and improved bioactivity.

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Section: Z-selective Rcm Of Peptidesmentioning

confidence: 99%

Synthesis of Cyclic Peptides and Peptidomimetics by Metathesis Reactions

Rijkers

2015

Topics in Heterocyclic Chemistry

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“…A more recent review of the synthetic applications of Z-selective cyclometalated ruthenium catalysts has also been revealed [43]. Initial investigations into the homodimerization of olefins utilized 4 ( Table 1, entries 1 and 5) [44]. A wide substrate scope was tolerated such as alcohols, amines, esters, and ethers (selected examples to compare catalysts are found in Table 1).…”

Section: Cyclometalated Catalysts Developmentmentioning

confidence: 99%

“…Furthermore, a high concentration of olefin was required for good reactivity, which could aid in catalyst initiation. These transformations were performed under static vacuum to promote removal Initial investigations into the homodimerization of olefins utilized 4 ( Table 1, entries 1 and 5) [44]. A wide substrate scope was tolerated such as alcohols, amines, esters, and ethers (selected examples to compare catalysts are found in Table 1).…”

Section: Cyclometalated Catalysts Developmentmentioning

confidence: 99%

Recent Advancements in Stereoselective Olefin Metathesis Using Ruthenium Catalysts

2017

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Olefin metathesis is a prevailing method for the construction of organic molecules. Recent advancements in olefin metathesis have focused on stereoselective transformations. Ruthenium olefin metathesis catalysts have had a particularly pronounced impact in the area of stereoselective olefin metathesis. The development of three categories of Z-selective olefin metathesis catalysts has made Z-olefins easily accessible to both laboratory and industrial chemists. Further design enhancements to asymmetric olefin metathesis catalysts have streamlined the construction of complex molecules. The understanding gained in these areas has extended to the employment of ruthenium catalysts to stereoretentive olefin metathesis, the first example of a kinetically E-selective process. These advancements, as well as synthetic applications of the newly developed catalysts, are discussed.

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“…While 7 displayed reduced activity in comparison to 5, enhanced Z selectivity in metathesis reactions was observed. For example, in the homodimerization of simple terminal olefins, 7 achieved levels of Z selectivity (greater than 90% in most cases) comparable to Mo-and W-based catalysts (specific examples will follow) [25]. It should also be noted that the thiolate catalysts developed by Jensen are capable of similar selectivities in these reactions, but tend to exhibit reduced selectivity for olefin metathesis over reactions such as olefin isomerization [19,21].…”

Section: Summary Of Substituent Effectsmentioning

confidence: 99%

Diastereocontrol in Olefin Metathesis: the Development of Z ‐Selective Ruthenium Catalysts

Keitz

2015

Handbook of Metathesis

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The diastereocontrol of the double bond formed during an olefin metathesis reaction has been a long-standing goal and challenge for the field. Only within the past few years have molybdenum (Mo), tungsten (W), and ruthenium (Ru) catalysts been able to achieve the level of stereocontrol necessary for synthetic applications. This chapter will focus on the development of Ru-based, Z-selective olefin metathesis catalysts, and consists of my personal account of the initial discoveries, as well as our current mechanistic understanding of the catalysts available. Examples of the potential synthetic uses for these catalysts will also be discussed. Due to the relative youth of this subfield of olefin metathesis, discoveries are being made at a rapid pace; thus, it is impractical to include the very latest results in this chapter. Nevertheless, I will attempt to demonstrate the potential applications of these new Ru catalysts, as well as address some of the synthetic limitations that remain. Molybdenum and tungsten Z-selective catalysts are discussed in Chapter 1, and also see Grubbs, Handbook of Metathesis, 2nd Edition, Volume 2, Chapter 7. The Challenge of Z-Selective Olefin MetathesisIn the quintessential description of an olefin metathesis reaction, two terminal olefins are reacted in the presence of a catalyst to form a new internal olefin and ethylene gas (Scheme 3.1). Importantly, metathesis is a thermodynamically controlled reaction that requires a driving force, such as the release of ring strain or the formation of a volatile small molecule product, in order to reach completion [1]. An additional consequence of thermodynamic control and the reversibility of the metathesis reaction is the formation of the thermodynamically most stable product or product mixture. In the case of internal olefins, the most stable product is typically the trans, or E, olefin [2]. Thus, in reactions like the one presented in

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Z-Selective Homodimerization of Terminal Olefins with a Ruthenium Metathesis Catalyst

Cited by 153 publications

References 31 publications

Synthesis of Cyclic Peptides and Peptidomimetics by Metathesis Reactions

Synthesis of Cyclic Peptides and Peptidomimetics by Metathesis Reactions

Recent Advancements in Stereoselective Olefin Metathesis Using Ruthenium Catalysts

Diastereocontrol in Olefin Metathesis: the Development of Z ‐Selective Ruthenium Catalysts

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