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Volumn 54, Issue 6, 2015, Pages 1881-1884

Hypervalent iodine reagents enable chemoselective deboronative/decarboxylative alkenylation by photoredox catalysis

Author keywords

Alkenes; Chemoselectivity; Hypervalent compounds; Photochemistry; Ruthenium

Indexed keywords

ALKENYLATION; CHEMICAL REACTIONS; FUNCTIONAL GROUPS; HYDROCARBONS; OLEFINS; PHOTOCHEMICAL REACTIONS; RUTHENIUM;

EID: 84964264752     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201410176     Document Type: Article
Times cited : (166)

References (60)
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    • A. Rudolph, M. Lautens, Angew. Chem. Int. Ed. 2009, 48, 2656 - 2670; Angew. Chem. 2009, 121, 2694-2708.
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    • Rudolph, A.1    Lautens, M.2
  • 14
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    • Vinyl carboxylic acid bound to a noncyclic iodine(III) reagent was reported before, however the reactivity of alkyl radical addition and decarboxylation was unknown
    • Vinyl carboxylic acid bound to a noncyclic iodine(III) reagent was reported before, however the reactivity of alkyl radical addition and decarboxylation was unknown:
  • 34
    • 84964264332 scopus 로고    scopus 로고
    • K2S2O8 oxidizes alkyl boronates to alkyl R radicals and engages in alkynylation with BI-alkyne, see Refs.[9] and [7b]. Its inability for alkenylation also suggests the formation of a BI complex similar to BI-alkyne. See Schemes S6, S15, and Table S1
    • K2S2O8 oxidizes alkyl boronates to alkyl R radicals and engages in alkynylation with BI-alkyne, see Refs.[9] and [7b]. Its inability for alkenylation also suggests the formation of a BI complex similar to BI-alkyne. See Schemes S6, S15, and Table S1.
  • 35
    • 84964198821 scopus 로고    scopus 로고
    • The reduction of BI-OCOR by photoexcited [RuII] is very slow (see Scheme S4), which implies that it is not the major reaction pathway for generating benziodoxole radicals
    • The reduction of BI-OCOR by photoexcited [RuII] is very slow (see Scheme S4), which implies that it is not the major reaction pathway for generating benziodoxole radicals.
  • 36
    • 66149154557 scopus 로고    scopus 로고
    • A radical a-addition to vinyl carboxylates was observed before. See
    • A radical a-addition to vinyl carboxylates was observed before. See: S. Martinet , A.Meou, P.Brun, Eur. J. Org. Chem. 2009, 2306 - 2311;
    • (2009) Eur. J. Org. Chem. , pp. 2306-2311
    • Martinet, S.1    Meou, A.2    Brun, P.3
  • 37
    • 77249159352 scopus 로고    scopus 로고
    • The radical aaddition was also confirmed by a 13C-labeling experiment; see Scheme S16. A b-addition to Michael acceptors was observed in the previous iridium photocatalyst system. See Refs. [8a,b], which suggests the distinction between these two photoredox systems
    • Y. Abe, T. Sawada, M. Takafuji, T. Mashimo, M. Ono, H. Ihara, Chem. Lett. 2010, 39, 174 - 175. The radical aaddition was also confirmed by a 13C-labeling experiment; see Scheme S16. A b-addition to Michael acceptors was observed in the previous iridium photocatalyst system. See Refs. [8a,b], which suggests the distinction between these two photoredox systems.
    • (2010) Chem. Lett. , vol.39 , pp. 174-175
    • Abe, Y.1    Sawada, T.2    Takafuji, M.3    Mashimo, T.4    Ono, M.5    Ihara, H.6
  • 38
    • 84964210429 scopus 로고    scopus 로고
    • For leading examples on benziodoxole radical, see
    • For leading examples on benziodoxole radical, see:
  • 44
    • 84964309336 scopus 로고    scopus 로고
    • It is unclear at this point if the effective reaction of cyclic iodine(III) compared to noncyclic iodine(III) reagents is due to the reactivity of the benziodoxole vinyl carboxylic acid complex, or the benziodoxole radical, or other reasons
    • It is unclear at this point if the effective reaction of cyclic iodine(III) compared to noncyclic iodine(III) reagents is due to the reactivity of the benziodoxole vinyl carboxylic acid complex, or the benziodoxole radical, or other reasons.
  • 45
    • 84964238327 scopus 로고    scopus 로고
    • The previously reported transition-metal-catalyzed alkyl radical addition to vinyl carboxylic acids involved internal singleelectron transfer to generate carbocations; see Ref.3
    • The previously reported transition-metal-catalyzed alkyl radical addition to vinyl carboxylic acids involved internal singleelectron transfer to generate carbocations; see Ref.3.
  • 55
  • 58
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    • The alkyl-substituted vinyl carboxylic acids gave no alkenylation product, possibly because the resulting radical was not stabilized; see Scheme S18. Similar results were observed in other alkyl Heck-type reactions as well; see Ref.19
    • The alkyl-substituted vinyl carboxylic acids gave no alkenylation product, possibly because the resulting radical was not stabilized; see Scheme S18. Similar results were observed in other alkyl Heck-type reactions as well; see Ref.19.
  • 59
    • 84893555273 scopus 로고    scopus 로고
    • This report is mechanistically different from decarboxylative trifluoromethylation of vinyl carboxylates using Togni reagents: See Scheme S10
    • This report is mechanistically different from decarboxylative trifluoromethylation of vinyl carboxylates using Togni reagents: P. Xu, A. Abdukader, K. Hu, Y. Cheng, C. Zhu, Chem. Commun. 2014, 50, 2308 - 2310. See Scheme S10.
    • (2014) Chem. Commun. , vol.50 , pp. 2308-2310
    • Xu, P.1    Abdukader, A.2    Hu, K.3    Cheng, Y.4    Zhu, C.5
  • 60
    • 84964269306 scopus 로고    scopus 로고
    • CCDC cd214216 (9) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
    • CCDC cd214216 (9) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data-request/cif


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.