A tutorial review of stereoretentive olefin metathesis based on ruthenium dithiolate catalysts

Abstract

Stereoretentive olefin metathesis based on ruthenium dithiolate complexes has become a very active field of research within the past years. This unique catalyst class is able to kinetically produce both Z- and E-alkenes in high stereochemical purity (typically >95:5) starting from stereochemically pure Z- or E-alkenes. The aim of this tutorial review is to organize the reported information concerning ruthenium dithiolate catalysts in a logic manner, thus providing an "operators handbook" for chemists who wish to apply this methodology in synthesis.

Application of New Efficient Hoveyda–Grubbs Catalysts Comprising an N→Ru Coordinate Bond in a Six-Membered Ring for the Synthesis of Natural Product-Like Cyclopenta[b]furo[2,3-c]pyrroles

“…The discovery of metathesis reactions has allowed the noticeable expansion of possibilities for the transformation of different unsaturated substrates, including those aimed at obtaining complex naturally occurring compounds and pharmacologically meaningful molecules, which is reflected in a number of recent reviews [ 1 , 2 , 3 , 4 , 5 , 6 , 7 , 8 ]. In particular, the ring-rearrangement metathesis (RRM) of bi- and polycyclic alkenes has made it possible to obtain systems that are practically inaccessible by means of other synthetic pathways [ 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 ].…”

“…The discovery of metathesis reactions has allowed the noticeable expansion of possibilities for the transformation of different unsaturated substrates, including those aimed at obtaining complex naturally occurring compounds and pharmacologically meaningful molecules, which is reflected in a number of recent reviews [1][2][3][4][5][6][7][8]. In particular, the ring-rearrangement metathesis (RRM) of biand polycyclic alkenes has made it possible to obtain systems that are practically inaccessible by Moreover, among all the variety of metathesis products known to date, there is a sole successful example of the HG-catalyzed RRM of 3a,6-epoxyisondole 1 which has produced the previously unknown heterocyclic system of cyclopenta [b]furo [2,3-c]pyrrole 2, but in modest yield (31%) [24] (Scheme 2).…”

Stereoretentive Ring-Opening Metathesis Polymerization to Access All-cis Poly(p-phenylenevinylene)s with Living Characteristics

“…[18][19][20] The trans alkenes are postulated to arise from isomerization driven by the catalyst during ROMP. We hypothesized that either Z-selective 21 or stereoretentive [22][23][24] metathesis catalysts could allow for the controlled preparation of all-cis PPVs with predictable high Mn's, low Đ's, and little to no trans defects. While Z-selective catalyst 2c has been applied to polymerize a variety of norbornene derivatives, 25 stereoretentive dithiolate-chelated Ru catalysts such as 2d have seldomly been used for ROMP.…”

Stereoretentive Olefin Metathesis: A New Avenue for the Synthesis of All-cis Poly(p-phenylene vinylene)s and Stereo­defined Polyalkenamers

“…The family of dithiolate Ru catalysts was therefore dubbed 'stereoretentive'. 5,18 The key differences in the modes of action of Z-selective and stereoretentive Ru catalysts are highlighted in Scheme 1 (adapted from Grubbs and Stoltz). 19 In Z-selective olefin metathesis, the catalyst delivers an olefin product with a high Z-alkene content from a terminal olefin starting material.…”