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(a) Sammes P.G., Dodsworth D.J. J. Chem. Soc., Chem. Commun. 1979;33-34 (b) Dodsworth D.J., Calcagno M.-P., Ehrmann E.U., Devadas B., Sammes P.G. J. Chem. Soc., Perkin Trans. 1. 1981;2120-2124. For examples of this reaction in the total synthesis of natural products, see: (c) Townsend C.A., Davis S.G., Christensen S.B., Link J.C., Lewis C.P. J. Am. Chem. Soc. 103:1981;6885-6888 (d) Townsend C.A., Christensen B.S., Davis S.G. J. Chem. Soc., Perkin Trans. 1. 1988;839-861 (e) Townsend C.A., Isomura Y., Davis S.G., Hodge J.A. Tetrahedron. 45:1989;2263-2276 (f) Graybill T.L., Pal K., Mc Guire S.M., Brobst S.W., Townsend C.A. J. Am. Chem. Soc. 111:1989;8306-8308 (g) Graybill T.L., Cassilas E.G., Pal K., Townsend C.A. J. Am. Chem. Soc. 121:1999;7729-7746.
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(a) Sammes P.G., Dodsworth D.J. J. Chem. Soc., Chem. Commun. 1979;33-34 (b) Dodsworth D.J., Calcagno M.-P., Ehrmann E.U., Devadas B., Sammes P.G. J. Chem. Soc., Perkin Trans. 1. 1981;2120-2124. For examples of this reaction in the total synthesis of natural products, see: (c) Townsend C.A., Davis S.G., Christensen S.B., Link J.C., Lewis C.P. J. Am. Chem. Soc. 103:1981;6885-6888 (d) Townsend C.A., Christensen B.S., Davis S.G. J. Chem. Soc., Perkin Trans. 1. 1988;839-861 (e) Townsend C.A., Isomura Y., Davis S.G., Hodge J.A. Tetrahedron. 45:1989;2263-2276 (f) Graybill T.L., Pal K., Mc Guire S.M., Brobst S.W., Townsend C.A. J. Am. Chem. Soc. 111:1989;8306-8308 (g) Graybill T.L., Cassilas E.G., Pal K., Townsend C.A. J. Am. Chem. Soc. 121:1999;7729-7746.
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(a) Sammes P.G., Dodsworth D.J. J. Chem. Soc., Chem. Commun. 1979;33-34 (b) Dodsworth D.J., Calcagno M.-P., Ehrmann E.U., Devadas B., Sammes P.G. J. Chem. Soc., Perkin Trans. 1. 1981;2120-2124. For examples of this reaction in the total synthesis of natural products, see: (c) Townsend C.A., Davis S.G., Christensen S.B., Link J.C., Lewis C.P. J. Am. Chem. Soc. 103:1981;6885-6888 (d) Townsend C.A., Christensen B.S., Davis S.G. J. Chem. Soc., Perkin Trans. 1. 1988;839-861 (e) Townsend C.A., Isomura Y., Davis S.G., Hodge J.A. Tetrahedron. 45:1989;2263-2276 (f) Graybill T.L., Pal K., Mc Guire S.M., Brobst S.W., Townsend C.A. J. Am. Chem. Soc. 111:1989;8306-8308 (g) Graybill T.L., Cassilas E.G., Pal K., Townsend C.A. J. Am. Chem. Soc. 121:1999;7729-7746.
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(a) Sammes P.G., Dodsworth D.J. J. Chem. Soc., Chem. Commun. 1979;33-34 (b) Dodsworth D.J., Calcagno M.-P., Ehrmann E.U., Devadas B., Sammes P.G. J. Chem. Soc., Perkin Trans. 1. 1981;2120-2124. For examples of this reaction in the total synthesis of natural products, see: (c) Townsend C.A., Davis S.G., Christensen S.B., Link J.C., Lewis C.P. J. Am. Chem. Soc. 103:1981;6885-6888 (d) Townsend C.A., Christensen B.S., Davis S.G. J. Chem. Soc., Perkin Trans. 1. 1988;839-861 (e) Townsend C.A., Isomura Y., Davis S.G., Hodge J.A. Tetrahedron. 45:1989;2263-2276 (f) Graybill T.L., Pal K., Mc Guire S.M., Brobst S.W., Townsend C.A. J. Am. Chem. Soc. 111:1989;8306-8308 (g) Graybill T.L., Cassilas E.G., Pal K., Townsend C.A. J. Am. Chem. Soc. 121:1999;7729-7746.
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32 seems to be a special case. However, this new method may be valuable for other brominations of acid-sensitive substrates, and the AcOH/NaOAc-solvent system proved to be as reliable as traditional solvents or even superior in many NBS experiments, especially for mono-brominations. For a NBS-bromination in acetic acid under ultrasound, see: Because brominations of acetal-protected benzaldehydes had not been described in the literature, we prepared various dioxane- or dioxolane-protected methoxymethoxy- and anisaldehydes and investigated their bromination: most of the acetales were resistant to hydrolysis during the brominations with NBS in chlorinated or polar aprotic solvents, and the sensitivity of dioxane
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Because brominations of acetal-protected benzaldehydes had not been described in the literature, we prepared various dioxane- or dioxolane-protected methoxymethoxy- and anisaldehydes and investigated their bromination: most of the acetales were resistant to hydrolysis during the brominations with NBS in chlorinated or polar aprotic solvents, and the sensitivity of dioxane 32 seems to be a special case. However, this new method may be valuable for other brominations of acid-sensitive substrates, and the AcOH/NaOAc-solvent system proved to be as reliable as traditional solvents or even superior in many NBS experiments, especially for mono-brominations. For a NBS-bromination in acetic acid under ultrasound, see: Paul V., Sudalai A., Daniel T., Srinivasan K.V. Synth. Commun. 25:1995;2401.
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