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Volumn 351, Issue 6, 2009, Pages 869-873

Sequential copper-catalyzed rearrangement-allylic substitution of bicyclic hydrazines with grignard reagents

Author keywords

Allylic alkylation; Copper; Grignard reagents; Rearrangement; Sequential reactions

Indexed keywords


EID: 65249097325     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200900037     Document Type: Article
Times cited : (27)

References (29)
  • 3
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    • T. Ainai, Y.-G. Wang, Y. Tokoro, Y. Kobayashi, J. Org. Chem. 2004, 69, 655-659; see also:
    • a) T. Ainai, Y.-G. Wang, Y. Tokoro, Y. Kobayashi, J. Org. Chem. 2004, 69, 655-659; see also:
  • 4
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    • and references cited therein
    • b) Y. Kobayashi, K. Nakata, T. Ainai, Org. Lett. 2005, 7, 183-186, and references cited therein.
    • (2005) Org. Lett , vol.7 , pp. 183-186
    • Kobayashi, Y.1    Nakata, K.2    Ainai, T.3
  • 14
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    • F. Menard, M. Lautens, Angew. Chem. 2008, 120, 2115-2118; Angew. Chem. Int. Ed. 2008, 47, 2085-2088;
    • i) F. Menard, M. Lautens, Angew. Chem. 2008, 120, 2115-2118; Angew. Chem. Int. Ed. 2008, 47, 2085-2088;
  • 16
    • 0037076930 scopus 로고    scopus 로고
    • 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
    • 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.
  • 20
    • 65249191068 scopus 로고    scopus 로고
    • 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.
    • 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.
  • 21
    • 65249138458 scopus 로고    scopus 로고
    • 3 and Josiphos-type ligands gave a similar acceleration of the rearrangement. On the other hand, Monophos and triethyl phosphite delayed the rearrangement.
    • 3 and Josiphos-type ligands gave a similar acceleration of the rearrangement. On the other hand, Monophos and triethyl phosphite delayed the rearrangement.
  • 22
    • 0036532452 scopus 로고    scopus 로고
    • 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
    • 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.
    • (2002) Tetrahedron , vol.58 , pp. 2701-2724
    • Agami, C.1    Couty, F.2
  • 23
    • 65249119906 scopus 로고    scopus 로고
    • 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.
    • 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.
  • 24
    • 65249170285 scopus 로고    scopus 로고
    • 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.
    • 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.
  • 26
    • 0141440704 scopus 로고    scopus 로고
    • and pertinent references cited therein. For copper directed allylic substitutions, see
    • For copper directed allylic substitutions, see: B. Breit, P. Demel, Adv. Synth. Catal. 2001, 343, 429-432, and pertinent references cited therein.
    • (2001) Adv. Synth. Catal , vol.343 , pp. 429-432
    • Breit, B.1    Demel, P.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.