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. 2009;48(16):2830-4.
doi: 10.1002/anie.200804651.

Beyond Reppe: building substituted arenes by [2+2+2] cycloadditions of alkynes

Brandon R Galan  1 , Tomislav Rovis
Affiliations

Beyond Reppe: building substituted arenes by [2+2+2] cycloadditions of alkynes

Brandon R Galan et al. Angew Chem Int Ed Engl. 2009.

Abstract

Synthetic sequel: The transition-metal-catalyzed [2+2+2] cycloaddition is an established method for the construction of carbocyclic frameworks but is often plagued by poor selectivity. Recent literature paints a promising picture--a more general metal-catalyzed [2+2+2] cycloaddition can be accomplished intermolecularly using three separate alkynes to furnish highly substituted arenas (see scheme).

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Figures

Figure 1
Figure 1
Conceptual approach to benzene synthesis
Figure 2
Figure 2
Example of an intra- and intermolecular metal-catalyzed [2+2+2] cycloaddition
Figure 3
Figure 3
Ru-catalyzed cyclotrimerization using a temporary boron tether
Figure 4
Figure 4
Pd-catalyzed carbonylation of the arylboronate intermediate
Figure 5
Figure 5
Cobalt-catalyzed [2+2+2] cycloaddition
Figure 6
Figure 6
Rh-catalyzed intermolecular [2+2+2] cycloaddition
Figure 7
Figure 7
Ligand controlled product formation of an Ir-catalyzed [2+2+2] cycloaddition
Figure 8
Figure 8
Mn-catalyzed [2+2+2] cycloaddition of 1,3-dicarbonyls with terminal acetylenes
Figure 9
Figure 9
Proposed pathway of Mn-catalyzed [2+2+2] cycloaddition of 1,3-dicarbonyls with terminal acetylenes13
Figure 10
Figure 10
Re catalyzed pyrone synthesis/[4+2]/retro-[4+2]
Figure 11
Figure 11
Rh-catalyzed cycloaddition using enol acetates as alkyne surrogates
Figure 12
Figure 12
Cationic rhodium-catalyzed cycloaddition using enol acetate
See this image and copyright information in PMC

References

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    1. Suzuki D, Urabe H, Sato F. J. Am. Chem. Soc. 2001;123:7925–7926. For the synthesis of substituted pyridines from nitriles see: b) Suzuki D, Nobe Y, Watai Y, Tanaka R, Takayama Y, Sato F, Urabe H. J. Am. Chem. Soc. 2005;127:7474–7479. Tanaka R, Yuza A, Watai Y, Suzuki D, Takayama Y, Sato F, Urabe H. J. Am. Chem. Soc. 2005;127:7774–7780.

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