Cu(I) β-diketiminates for alkene aziridination:: Reversible Cu-arene binding and catalytic nitrene transfer from Phl=NTs

被引：65

作者：

Amisial, LD ^{[1
]}

Dai, XL ^{[1
]}

Kinney, RA ^{[1
]}

Krishnaswamy, A ^{[1
]}

Warren, TH ^{[1
]}

机构：

[1] Georgetown Univ, Dept Chem, Washington, DC 20057 USA

来源：

INORGANIC CHEMISTRY | 2004年 / 43卷 / 21期

关键词：

D O I：

10.1021/ic048968+

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

beta-Diketiminato Cu(I)-lutidine complexes [RMeNN]Cu(2,4-lutidine) (R = Me (4a), Pr-i (4b)) were prepared in high yield from TI[RMeNN] and [CuBr(2,4-lutidine)(2)](2). Both 4a and 4b reversibly dissociate lutidine base in toluene to give [RMeNN]Cu(toluene) solvento complexes. A related base-free dicopper species {[Me2NN]Cu}(2) (6) bridged via eta(2)-binding of opposing N-aryl rings could be isolated by the addition of TI[Me2NN] to CuBr. The lutidine precursors serve as precatalysts for the aziridination of alkenes with PhI=NTs. Styrene, beta-methylstyrene, and cyclooctene gave the highest yields (59-96%) with a low olefin to Phl=NTs ratio (3:1) and 5 mol % catalyst loading.

引用

页码：6537 / 6539

页数：3

共 37 条

[31] Enantioselective catalytic aziridinations and asymmetric nitrene insertions into CH bonds
Müller, P
Fruit, C
[J]. CHEMICAL REVIEWS, 2003, 103 (08) : 2905 - 2919
[32] A COPPER(I) CATALYST FOR CARBENE AND NITRENE TRANSFER TO FORM CYCLOPROPANES, CYCLOPROPENES, AND AZIRIDINES
PEREZ, PJ
BROOKHART, M
TEMPLETON, JL
[J]. ORGANOMETALLICS, 1993, 12 (02) : 261 - 262
[33] Structural origins of a dramatic variation in catalyst efficiency in enantioselective alkene aziridination: Implications for design of ligands based on chiral biaryldiamines
Sanders, CJ
Gillespie, KM
Bell, D
Scott, P
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (29) : 7132 - 7133
[34] Copper chemistry of β-diketiminate ligands:: Monomer/dimer equilibria and a new class of bis(μ-oxo)dicopper compounds
Spencer, DJE
Reynolds, AM
Holland, PL
Jazdzewski, BA
Duboc-Toia, C
Le Pape, L
Yokota, S
Tachi, Y
Itoh, S
Tolman, WB
[J]. INORGANIC CHEMISTRY, 2002, 41 (24) : 6307 - 6321
[35] β-diketiminate ligand backbone structural effects on Cu(I)/O2 reactivity:: Unique copper-superoxo and bis(μ-oxo) complexes
Spencer, DJE
Aboelella, NW
Reynolds, AM
Holland, PL
Tolman, WB
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (10) : 2108 - 2109
[36] Angular ligand constraint yields an improved olefin aziridination catalyst
Vedernikov, AN
Caulton, KG
[J]. ORGANIC LETTERS, 2003, 5 (15) : 2591 - 2594
[37] A new β-diketiminate ligand carrying a functional group on the carbon framework.: Synthesis and characterization of a linear polymeric copper(I) complex
Yokota, S
Tachi, Y
Nishiwaki, N
Ariga, M
Itoh, S
[J]. INORGANIC CHEMISTRY, 2001, 40 (21) : 5316 - 5317

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