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Volumn 50, Issue 20, 2011, Pages 4671-4674

Mizoroki-heck-type reaction mediated by potassium tert-butoxide

Author keywords

alkenes; aryl radicals; C C coupling; single electron transfer; synthetic methods

Indexed keywords

ALKENES; ARYL RADICALS; C-C COUPLING; SINGLE-ELECTRON TRANSFER; SYNTHETIC METHODS;

EID: 79955645452     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201008220     Document Type: Article
Times cited : (150)

References (34)
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    • The Mizoroki-Heck reaction catalyzed by a metal other than palladium is also known but is rare. For a review, see:, in (Ed.: M. Oestreich), Wiley, Chichester, pp.a
    • The Mizoroki-Heck reaction catalyzed by a metal other than palladium is also known but is rare. For a review, see:, L. Ackermann, R. Born, in Mizoroki-Heck Reaction (Ed.:, M. Oestreich,), Wiley, Chichester, 2009, pp. 383-403.
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    • KOtBu in combination with or without a bidentate nitrogen-containing ligand is used in the coupling of aryl halides with (hetero)arenes, where generation of aryl radicals from aryl halides is considered to be involved
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    • note
    • For the reactions shown in Tablea 1-Tablea 3, KOtBu, which was purchased from Wako Pure Chemicals Industries, Ltd. (product number 163-08425), was used as received. Its ICP-AES and ICP-MS analysis showed that the contents of Co, Ni, Ru, Rh, Pd, Ag, Ir, Pt, and Au are less than 0.05a ppm and those of Fe and Cu are 1.0a ppm and 1.1a ppm, respectively. See also Ref.a [8].
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    • note
    • The reaction using a sublimed grade KOtBu (99.99 % purity, Aldrich Co., product number 659878) or a KOtBu purified through sublimation by us gave coupling product 3 ao in a similar yield (80 % or 79 % yield, respectively). The contents of Fe and Cu in the sublimed KOtBu are <0.2a ppm (under detection limit) and 0.25a ppm, respectively (ICP-AES analysis). These results amply indicate that the coupling is promoted by KOtBu itself rather than catalyzed by contaminated transition metals. We asked Dr. Kazufumi Kohno to repeat the reaction and he confirmed that the reaction under the same conditions gave 3 ao in 71 % yield.
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    • note
    • N,N-Dimethylacetamide and dimethylsulfoxide also were effective as solvents but addition of their enolates to styrene and the coupling products took place and thus the yield of 3 ao was slightly lower than that obtained when DMF was used.
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    • note
    • The products are all Ea isomers. The corresponding Za isomer or 1,1-disubstitued product was not observed in any reaction in Tablea 2.
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    • note
    • A large amount of biphenyls having a tert-butoxy, dimethylamino, or hydroxy group at the 3- or 4-positions, all of which are most likely to be produced through 4-phenylbenzyne, was observed as by-products. These by-products were produced also in the coupling reaction but in lower amounts.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.