The first asymmetric synthesis of optically active tropilidenes. Highly regio- and diastereo-differentiating addition of diazo ester to aromatic ring using 2,4-pentanediol as chiral linking bridge

Chemistry Letters

Volumn , Issue 1, 1998, Pages 45-46

  Sugimura, Takashi ^a   Nagano, Shinya ^a   Tai, Akira ^a  

^a UNIVERSITY OF HYOGO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0032376354     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.1998.45     Document Type: Article

References (26)

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21. For a recent example of the intramolecular cycloadditions with diazo esters forming medium size rings, see: M. P. Doyle, M. N. Protopopova, C. S. Peterson, and J. P. Vitale, J. Am. Chem. Soc., 118, 7865 (1996).
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23. When the reaction was carried out at higher concentration (50 mM), the fumaric diester by intermolecular diazo homo-coupling was also obtained in 2.4% yield.
24. 1H NMR analysis using the NOE technique and a shift reagent.
25. When the addition was carried out in acetonitrile, the ratio of 14 and the regioisomer was 1 to 1. The cycloaddition of 4 in acetonitrile also gave a regioisomer as 20% of the adduct. In all cases, the regioisomer was the TCNE adduct at the 3,6-positions and diastereomerically pure.
26. Heats of formation calculated by PM3 were -72.57 kcal/mol for 4 and -70.04 kcal/mol for 2 (R = H).