Alternating ROMP

Scheme 3.8 Alternating ROMP monomers exhibiting different steric demand and ring strain...

Fig. 3.31 Steric control in alternating ROMP Tendencies of norbomene and cyclooctene to give productive olefin metathesis upon coordination are illustrated by a thick arrow (preferred monomer) or a thin arrow (less favoured monomer) (a) only minor steric hindrance SlMes greatly favours the polymerisation of the strained norbomene (b) the rotating phenylethyl-group induces a steiically more congested active site, leading to preferred incorporation of the smaller cyclooctene (c) the flexible and small cyclooctene derived polymer fragment permits the incorporation of the bulky norbomene...

Bergens etal. described the construction of an initiator-containing organic framework that was produced by an alternating ROMP of ds-cyclooctene and... 

Figure 19.9 P,0-dichelating Grubbs-type initiators for the alternating ROMP of norborn-2-ene and cis-cyclooctene.

Figure 17 Two examples of catalysts designed for alternating ROMP based on steric parameters. Reproduced with permission from Bornand, M. Chen, P. Angew. Chem. Int Ed. 2005, 44, 7909 ...

One of the more complex applications of alternating ROMP to date was performed with cyclooctene and norbornene... 

Alternatively a non-metallated chelating monomer such as (227) or (228) may be copolymerized with (223) and the metal introduced post-polymerization. Using this strategy nanoclusters of silver,615 gold,616 ZnS617 and CdS618 have been prepared. A related approach has recently been adopted with the ROMP of norbornenes functionalized with crown ether, (229),619 and triazacy-clononane, (230),620 substituents. 

The first well-defined Ru alkylidene metathesis initiator, (231), was reported by Grubbs et al. in 1992.632 This complex initiates the ROMP of norbornene and other highly strained monomers such as bicyclo[3.2.0]hept-6-ene.633 Examination of alternative ligands634-636 led to the development of more active initiators, in particular (232)637 and (233).638-640... 

An alternative method for the preparation of polymer-chained pendant ligands has been recently developed.102 The polymerization of the (R)-hydroxylpiperidinyl fragment was realized by ROMP of a bicyclic olefin with the commercially available Grubbs catalyst. 

Catalytic processes using diazo chemistry and stoichiometric methods with Fischer carbenes are complimentary for the introduction of a substituted carbene into a molecule. For methylene addition, however, there is no viable alternative to the modified Simmons-Smith reaction. Ring-closing metathesis, and its ROMP counterpart, have matured so fast that even now they rank among the most useful synthetic methodologies in organic chemistry. 

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