Control of Olefin Geometry in Macrocyclic Ring-Closing Metathesis Using a Removable Silyl Group

Wang, Yikai; Jiménez, Miguel; Hansen, Anders S.; Raiber, Eun‐Ang; Schreiber, Stuart L.; Young, Damian W.

doi:10.1021/ja202012s

Cited by 70 publications

(27 citation statements)

References 56 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Recently, chemical compounds with different macrocyclic rings inside themselves have attracted more interests in different research fields, including synthetic chemistry, natural products, and chemical biology [13][14][15][16][17][18][19][20][21]. For example, as one of the most attractive drugs for cancer therapy, epothilones and their relatives have evoked a vast research effort within academic and pharmaceutical research groups that include numerous total and partial syntheses and extensive structure-activity relationship studies [15][16][17][18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

Effects of Alkali Metal Ion Cationization on Fragmentation Pathways of Triazole-Epothilone

Duan

Luo

Chen

et al. 2012

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

The collisionally activated dissociation mass spectra of the protonated and alkali metal cationized ions of a triazole-epothilone analogue were studied in a Fourier transform ion cyclotron resonance mass spectrometer. The fragmentation pathway of the protonated ion was characterized by the loss of the unit of C 3 H 4 O 3 . However, another fragmentation pathway with the loss of C 3 H 2 O 2 was identified for the complex ions with Na + , K + , Rb + , and Cs + . The branching ratio of the second pathway increases with the increment of the size of alkali metal ions. Theoretical calculations based on density functional theory (DFT) method show the difference in the binding position of the proton and the metal ions. With the increase of the radii of the metal ions, progressive changes in the macrocycle of the compound are induced, which cause the corresponding change in their fragmentation pathways. It has also been found that the interaction energy between the compound and the metal ion decreases with increase in the size of the latter. This is consistent with the experimental results, which show that cesiated complexes readily eject Cs + when subject to collisions.

show abstract

Section: Introductionmentioning

confidence: 99%

Effects of Alkali Metal Ion Cationization on Fragmentation Pathways of Triazole-Epothilone

Duan

Luo

Chen

et al. 2012

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

show abstract

“…5 Z-macrocycles have also been synthesized by reaction of terminal olefins with internal vinyl silanes followed by protodesilylation. 6 However, these approaches require multiple steps to synthesize the desired product, and thus more direct methods using olefin metathesis are desirable. In 2011, the first report of Z-selective RCM was disclosed.…”

mentioning

confidence: 99%

A Highly Efficient Synthesis of Z‐Macrocycles Using Stereoretentive, Ruthenium‐Based Metathesis Catalysts

Ahmed

Grubbs

2017

Angewandte Chemie

View full text Add to dashboard Cite

A highly efficient, Z‐selective ring‐closing metathesis system for the formation of macrocycles using a stereoretentive, ruthenium‐based catalyst supported by a dithiolate ligand is reported. The catalyst is remarkably active as observed in initiation experiments showing complete catalyst initiation at −20 °C within 10 minutes. Macrocyclization reactions generated Z‐products from easily accessible diene starting materials bearing a Z‐olefin moiety. This approach provides a more efficient and selective route to Z‐macrocycles relative to previously reported systems. Reactions were completed within shorter reaction times, and turnover numbers of up to 100 could be achieved. Macrocyclic lactones ranging in size from twelve‐ to seventeen‐membered rings were synthesized in moderate to high yields (67–79 %) with excellent Z‐selectivity (95–99 %).

show abstract

“…Indirect methods to deliver Z-olefins have been developed, such as alkyne metathesis and subsequent partial reduction of the alkyne [25,26]. There have also been substrate dependent methods for Zselectivity [27][28][29][30], but a universal method for Z-selective OM remained elusive.…”

Section: General Introductionmentioning

confidence: 99%

Recent Advancements in Stereoselective Olefin Metathesis Using Ruthenium Catalysts

2017

View full text Add to dashboard Cite

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.

show abstract

Control of Olefin Geometry in Macrocyclic Ring-Closing Metathesis Using a Removable Silyl Group

Cited by 70 publications

References 56 publications

Effects of Alkali Metal Ion Cationization on Fragmentation Pathways of Triazole-Epothilone

Effects of Alkali Metal Ion Cationization on Fragmentation Pathways of Triazole-Epothilone

A Highly Efficient Synthesis of Z‐Macrocycles Using Stereoretentive, Ruthenium‐Based Metathesis Catalysts

Recent Advancements in Stereoselective Olefin Metathesis Using Ruthenium Catalysts

Contact Info

Product

Resources

About