Reactions of Cyclic Diazoamides:Convenient Synthesis of Dispirocyclic Cyclopropane Systems

Abstract

Rhodium(II) acetate catalyzed intermolecular cyclopropanationreactions of cyclic diazoamides with exocyclic olefins are describedto furnish an assortment of stable strained dispirocyclic cyclopropanesystems in good yields under mild experimental conditions.

Key words

carbenoids - diazo compounds - indoles - rhodium - spiro compounds

References

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15

The structure of compounds 3d and 5b wereunequivocally corroborated by single crystal X-ray analyses andwill be disclosed in due course.

16

Crystal data for compound 6a: C₁₉H₂₃NO, M = 281.38,0.46 × 0.44 × 0.29 mm³, orthorhombic,space group P212121 with a = 7.658(3) Å, b = 13.287(5) Å, c = 15.731(7) Å, α = 90.00°, β = 90.00°, γ = 90.00°, V = 1600.7(11) ų, T = 293(2)K, R ₁ = 0.0528, wR ₂ = 0.1252on observed data, z = 4, D _calcd = 1.168g cm^-3, F(000) = 608,Absorption coefficient = 0.079 mm^-1, λ = 0.7107 Å,3478 reflections were collected on a Bruker’s SMART APEXsingle crystal CCD diffractometer, 3122 observed reflections [I ³2σ (I)]. The largest differencepeak and hole = 0.242 and -0.205e
Å^-3,respectively. The structure was solved by direct methods and refinedby full-matrix least squares on F ² using SHELXL-97software.

17

Crystallographic data for 6a has been deposited with the CambridgeCrystallographic Data Centre as supplementary publication no CCDC-202639.Copies of the data can be obtained free of charge on applicationto 12, Union Road, Cambridge CB2 1EZ, UK. (Fax: [phone];
e-mail:[e-mail]).

19

The possibility of formation of olefins 7 from the cyclopropane 6 byring opening under the experimental condition is ruled out by performingthe control experiments by reapplying the reaction conditions onthe isolated pure products 6.

21

Similar trend was also observed inour earlier studies of C-H insertion reactions using these cyclicdiazo carbonyl compounds. See ref. 13.