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Review
. 2010 Jun 11;15(6):4242-60.
doi: 10.3390/molecules15064242.

Construction of eight-membered carbocycles with trisubstituted double bonds using the ring closing metathesis reaction

Motoo Tori  1 , Reiko Mizutani
Affiliations
Review

Construction of eight-membered carbocycles with trisubstituted double bonds using the ring closing metathesis reaction

Motoo Tori et al. Molecules. .

Abstract

Medium sized carbocycles are particularly difficult to synthesize. Ring closing metathesis reactions (RCM) have recently been applied to construct eight-membered carbocycles, but trisubstituted double bonds in the eight-membered rings are more difficult to produce using RCM reactions. In this review, model examples and our own results are cited and the importance of the preparation of suitably designed precursors is discussed. Examples of RCM reactions used in the total synthesis of natural products are also outlined.

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Figures

Figure 1
Figure 1
Structures of the reagents for RCM reactions.
Scheme 1
Scheme 1
Cyclization to the dioxacyclooctene ring.
Scheme 2
Scheme 2
Attempt to cyclize a simple diene.
Scheme 3
Scheme 3
Attempts to cyclize fused systems.
Scheme 4
Scheme 4
Formation of azacyclooctene.
Scheme 5
Scheme 5
Cyclization to polyfunctional cyclooctene.
Scheme 6
Scheme 6
Cyclization to cyclooctene and cycloheptene.
Scheme 7
Scheme 7
Competition to oxacyclooctadiene and oxacyclohexene.
Scheme 8
Scheme 8
Cyclization of diene to benzoazacyclooctene.
Scheme 9
Scheme 9
Attempted cyclization of simple dienes to 7-, 8- and 9-membered carbocycles.
Scheme 10
Scheme 10
Tandem RCM to 7-membered carbocycle and ring opening to fused cyclooctene.
Scheme 11
Scheme 11
Cyclization to cyclooctene derivative, a part of the taxane skeleton.
Scheme 12
Scheme 12
Effect of the protecting group in the cyclization to cyclooctene.
Scheme 13
Scheme 13
Comparison of the catalysts and the solvents.
Scheme 14
Scheme 14
Olefin isomerization and the formation of a one-carbon less ketone.
Scheme 15
Scheme 15
Olefin isomerization and the formation of two ketones.
Scheme 16
Scheme 16
Olefin isomerization and the proposed mechanism.
Scheme 17
Scheme 17
Formation of the one-carbon less carbocycle with a trisubstituted double bond.
Scheme 18
Scheme 18
Synthesis of cyclooctene with a trisubstituted double bond.
Scheme 19
Scheme 19
Cyclooctene in the steroid-like ring system.
Scheme 20
Scheme 20
Tri-substituted double bond in the cyclooctene ring.
Scheme 21
Scheme 21
Tandem RCM and the ring opening of a three-membered ring.
Scheme 22
Scheme 22
Attempts to cyclize to cyclooctene with a tri-substituted double bond.
Scheme 23
Scheme 23
Attempts to synthesize cyclooctene.
Scheme 24
Scheme 24
The effects of the configuration of substrates.
Scheme 25
Scheme 25
The effect of the configuration of substrates.
Scheme 26
Scheme 26
The effect of the configuration of substrates.
Figure 2
Figure 2
Steric energies and conformations of 68, 80, and 117−119 calculated by CONFLEX.
Figure 2
Figure 2
Steric energies and conformations of 68, 80, and 117−119 calculated by CONFLEX.
Figure 3
Figure 3
Steric energies and conformations calculated for 107 and 111' by CONFLEX.
Figure 4
Figure 4
Steric energies and conformations calculated for 81−84 by CONFLEX.
Figure 5
Figure 5
Steric energies and conformations calculated for 63' and 65' by CONFLEX.
See this image and copyright information in PMC

References

    1. Nguyen S.T., Johnson L.K., Grubbs R.H. Ring-opening metathesis polymerization (ROMP) of norbornene by a group VIII carbene complex in protic media. J. Am. Chem. Soc. 1992;114:3974–3975.
    1. Nguyen S.T., Grubbs R.H. Syntheses and activities of new single-component, ruthenium-based olefin metathesis catalysis. J. Am. Chem. Soc. 1993;115:9858–9859.
    1. Grubbs R.H., Miller S.J., Fu G.C. Ring-closing metathesis and related processes in organic synthesis. Acc. Chem. Res. 1995;28:446–452. doi: 10.1021/ar00059a002. - DOI
    1. Schwab P., France M.B., Ziller J.W., Grubbs R.H. A series of well-defined metathesis catalysts-synthesis of [RuCl2(CHR)(PR3)2] and its reactions. Angew. Chem. Int. Ed. Engl. 1995;34:2039–2041. doi: 10.1002/anie.199520391. - DOI
    1. Schwab P., Grubbs R.H., Ziller J.W. Synthesis and applications of RuCl2(=CHR’)(PR3)2: The influence of the alkylidene moiety on metathesis activity. J. Am. Chem. Soc. 1996;118:100–110.

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