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The reaction of acylnitroso Diels-Alder cycloadducts with Grignard reagents catalyzed by copper salts gave only minor amounts of trans-1,4-hydroxamic acid derivatives: M. D. Surman, M. J. Mulvihill, M. J. Miller, J. Org. Chem. 2002, 67, 4115-4121.
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13C NMR analysis of p-Br-benzoyl- and p-nitrobenzoyl derivatives of compound 3c (see compounds 7-9 in Supporting Information), and the formation of addition products of types 5 and 6 (not bearing the carbamate protection on the nitrogen linked to the cyclopentene framework, see Table 2 and Scheme 2), indicate the necessary occurrence of a 5,5-fused ring system. After the preparation of this manuscript, X-ray crystallo-graphic proof on related derivatives was independently obtained by Mark Lautens and co-workers: b) A. Martins, S. Lemouzy, M. Lautens, Org. Lett. 2009, 11, 181-183.
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13C NMR analysis of p-Br-benzoyl- and p-nitrobenzoyl derivatives of compound 3c (see compounds 7-9 in Supporting Information), and the formation of addition products of types 5 and 6 (not bearing the carbamate protection on the nitrogen linked to the cyclopentene framework, see Table 2 and Scheme 2), indicate the necessary occurrence of a 5,5-fused ring system. After the preparation of this manuscript, X-ray crystallo-graphic proof on related derivatives was independently obtained by Mark Lautens and co-workers: b) A. Martins, S. Lemouzy, M. Lautens, Org. Lett. 2009, 11, 181-183.
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3 and Josiphos-type ligands gave a similar acceleration of the rearrangement. On the other hand, Monophos and triethyl phosphite delayed the rearrangement.
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3 and Josiphos-type ligands gave a similar acceleration of the rearrangement. On the other hand, Monophos and triethyl phosphite delayed the rearrangement.
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22
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0036532452
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However, an alternative stepwise mechanism in which the N-Boc protecting group acts as a nucleophile thus trapping an allylic cation intermediate cannot be ruled out. For a review on the reactivity of N-Boc protecting group, see
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However, an alternative stepwise mechanism in which the N-Boc protecting group acts as a nucleophile thus trapping an allylic cation intermediate cannot be ruled out. For a review on the reactivity of N-Boc protecting group, see: C. Agami, F. Couty, Tetrahedron 2002, 58, 2701-2724.
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65249119906
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For reviews, see: a B. Breit, P. Demel, in: Modern Organocopper Chemistry, (Ed.: N. Krause) Wiley-VCH, Weinheim, 2002, pp 188-223; b) A. S. E. Karlstrom, J.-E. Bäckvall, in: Modern Organocopper Chemistry, (Eds.: N. Krause) Wiley-VCH, Weinheim, 2002, pp. 259-288.
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For reviews, see: a) B. Breit, P. Demel, in: Modern Organocopper Chemistry, (Ed.: N. Krause) Wiley-VCH, Weinheim, 2002, pp 188-223; b) A. S. E. Karlstrom, J.-E. Bäckvall, in: Modern Organocopper Chemistry, (Eds.: N. Krause) Wiley-VCH, Weinheim, 2002, pp. 259-288.
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24
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65249170285
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The use of a reversed order of addition (i.e., the substrate lc was added to the in situ formed magnesium cuprate) gave a completely different product distribution. In this case an inseparable mixture of regioisomer-ic adducts bearing a double protection of the hydrazine moiety was obtained.
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The use of a reversed order of addition (i.e., the substrate lc was added to the in situ formed magnesium cuprate) gave a completely different product distribution. In this case an inseparable mixture of regioisomer-ic adducts bearing a double protection of the hydrazine moiety was obtained.
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26
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0141440704
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