Organic ring-closing metathesis

The last decade has witnessed the growing use of olehn metathesis in organic synthesis.Ring closing metathesis RCM, Eq. (6)] and ring opening metathesis [ROM, Eq. (7)1 as well as a combination of these transformations have resulted in providing opportunities to build molecules of interest and importance. 

The concept of performing microwave synthesis in room temperature ionic liquids (RTIL) as reaction media has been applied to several different organic transformations (Scheme 4.18), such as 1,3-dipolar cycloaddition reactions [54], catalytic transfer hydrogenations [55], ring-closing metathesis [56], the conversion of alcohols to alkyl halides [57, 58], and several others [59-61],... 

Catalytic olefin metathesis, in only a few years, has risen to be one of the most important and reliable processes in organic synthesis. Recently, several reports by Schrock and Hoveydallsbbond forming transformations efficiently and enan-tioselectively. A recent concise and enantioselective synthesis of exo-brevicomin by Burke utilizes chiral catalyst 91 (Scheme 13) to effect the desymmetriza-tion of 90 through a ring-closing metathesis.11531... 

The ring closing metathesis is used for the synthesis of heterocycles [263], analogs of peptides (Scheme 3.20) [264] and natural [181] in solid-phase organic... 

I 7 7 Polymer-supported Otejin Metathesis Catalysts for Organic and Combinatorial Synthesis Tab. 11.3 Recycling of Ru complex (16) in the ring-closing metathesis of diene (17). 

Ring-closing metathesis of an enyne, which has double and triple bonds in the molecule, is a remarkable reaction which is useful in synthetic organic chemistry. In enyne metathesis, the double bond is cleaved and carbon-carbon bond formation occurs between the double and triple bonds. The cleaved alkylidene part is moved to the alkyne carbon. Thus, the cyclized compound formed in this reaction has a diene moiety [Eq. (6.77)]. The reaction is also called skeletal rearrangement and is induced by Pt, Pd, Ga, and Ru catalysts ... 

Piscopio AD, Miller JF, Koch K (1999) Ring closing metathesis in organic synthesis evolution of a high speed, solid phase method for the preparation of P-tum mimetics. Tetrahedron 55 8189-8198... 

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. 

Kevin J. Quinn of the College of the Holy Cross chose (Organic Lett. 2005, 7, 1243) a complementary approach in his synthesis of rollicosin. The symmetrical diol 4 is also available from carbohydrate precursors. Monosilylation followed by esterification with acryloyl chloride gave 5. Exposure of 5 to the Grubbs catalyst in the presence of 6 led, by ring-closing metathesis and cross metathesis, to the y-lactonc 7. Note that 5-lactone formation did not compete ... 

Ring-closing metathesis can also be used to close larger rings. In the course of a total synthesis of (-)-dactylolide, Michael P. Jennings of the Unversity of Alabama described (Organic Lett. 2005, 7,... 

Construction of organic nanotubes starting from porphyrin dendrimers with core/shell architecture is also feasible. Figure 8.29 also shows how covalent nanotubes can be produced by removal of the dendritic component of the molecule. A coordination polymer is first synthesised from a dendritic metallopor-phyrin with alkene end groups. This is subjected to intramolecular and intermo-lecular crosslinking by ring-closing metathesis at the periphery. 

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