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. 2010 Aug 1;66(33):6391-6398.
doi: 10.1016/j.tet.2010.04.094.

A Diels-Alder Route to Angularly Functionalized Bicyclic Structures

Woo Han Kim  1 , Jun Hee Lee, Baptiste Aussedat, Samuel J Danishefsky
Affiliations

A Diels-Alder Route to Angularly Functionalized Bicyclic Structures

Woo Han Kim et al. Tetrahedron. .

Abstract

A Diels-Alder based route to trans-fused angularly functionalized bicyclic structures has been developed. This transformation features the use of a tetrasubstituted dienophile in the cycloaddition step.

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Figures

Figure 1
Figure 1
Scheme 2
Scheme 2
aKey: (a) NaNO2, CAN, CH3CN, RT, 24 h, 56%; (b) toluene, 100 °C, 80 h, 78%; (c) n-Bu3SnH, AIBN, benzene, reflux, 2 h; (d) HF, CH3CN, 1 h.
Scheme 3
Scheme 3
aKey: (a) NaNO2, CAN, CH3CN, RT, 24 h, 61%; (b) toluene, 100 °C, 10 h, 95%; (c) n-Bu3SnH, AIBN, benzene, reflux, 2 h; (d) HF, CH3CN, 1 h; (e) toluene, 100 C, 36 h, 63%, d.r. = 4:1; (f) HF, CH3CN, RT, 8 h; (g) n-Bu3SnH, AIBN, benzene, reflux, 1.5 h, 48% for two steps.
Scheme 4
Scheme 4
aKey: (a) 2,6-di-tert-butyl-4-methylphenol, toluene, 130 °C, 24 h. (b) 2,6-di-tert-butyl-4-methylphenol, toluene, 150 °C, 24 h.
Scheme 5
Scheme 5
aKey: (a) Zn dust, THF/AcOH (2:1), −20 °C, 3 h; (b) AllocCl, THF, sat. NaHCO3, RT, 3 h.
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References

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