Catalytic 1,2-dihydronaphthalene and E-aryl-diene synthesis via CoIII-Carbene radical and o-quinodimethane intermediates

被引:47
作者
te Grotenhuis, Colet [1 ]
Das, Braja G. [1 ]
Kuijpers, Petrus F. [1 ]
Hageman, Wouter [1 ]
Trouwborst, Mees [1 ]
de Bruin, Bas [1 ]
机构
[1] Univ Amsterdam, Homogeneous Supramol & Bioinspired Catalysis HomK, Vant Hoff Inst Mol Sci HIMS, Sci Pk 904, NL-1098 XH Amsterdam, Netherlands
关键词
ORGANOLITHIUM REAGENTS; CONJUGATE ADDITION; SUBSTITUTED DIHYDRONAPHTHALENES; ASYMMETRIC CYCLOPROPANATION; STEREOSELECTIVE-SYNTHESIS; CONSTRUCTION; HAMIGERANS; BONDS; LASOFOXIFENE; GENERATION;
D O I
10.1039/c7sc03909c
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Catalytic synthesis of substituted 1,2-dihydronaphthalenes via metalloradical activation of o-styryl N-tosyl hydrazones ((E)-2-(prop-1-en-1-yl) benzene-N-tosyl hydrazones) is presented, taking advantage of the intrinsic reactivity of a cobalt(III)-carbene radical intermediate. The method has been successfully applied to a broad range of substrates with various R-1 substituents at the aromatic ring, producing the desired ring products in good to excellent isolated yields for substrates with an R-2 = COOEt substituent at the vinylic position (similar to 70-90%). Changing the R-2 moiety from an ester to other substituents has a surprisingly large influence on the (isolated) yields. This behaviour is unexpected for a radical rebound ring-closure mechanism, and points to a mechanism proceeding via ortho-quinodimethane (o-QDM) intermediates. Furthermore, substrates with an alkyl substituent on the allylic position reacted to form E-aryl-dienes in excellent yields, rather than the expected 1,2-dihydronaphthalenes. This result, combined with the outcome of supporting DFT calculations, strongly points to the release of reactive o-QDM intermediates from the metal centre in all cases, which either undergo a 6 pi-cyclisation step to form the 1,2dihydronaphthalenes, or a [1,7]-hydride shift to produce the E-aryl-dienes. Trapping experiments using TEMPO confirm the involvement of cobalt(III)-carbene radical intermediates. EPR spectroscopic spin-trapping experiments using phenyl N-tert-butylnitrone (PBN) confirm the radical nature of the catalytic reaction.
引用
收藏
页码:8221 / 8230
页数:10
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