Organic syntheses via transition metal complexes. 95. Rearrangement of (cyclobutenyl)carbene tungsten complexes to 1-tungsta-1,3,5-hexatrienes

被引：19

作者：

Aumann, R ^{[1
]}

Hildmann, B ^{[1
]}

Frohlich, R ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

ORGANOMETALLICS | 1998年 / 17卷 / 06期

关键词：

D O I：

10.1021/om9708586

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

(Cyclobutenyl)carbene tungsten complexes are shown to rearrange to 1-tungsta-1,3,5-hexatrienes. Azabicyclo[4.2.0]octadiene (bis)carbene tungsten complexes 3a-c, which served as model compounds in these studies, were generated by [4 + 2]- and [2 + 2] domino cycloaddition of 2 equiv of (l-alkynyl)carbene complex (CO)(5)W=C(OEt)C=CPh (1) to alkenyl imidates RCH=CHC(OEt)=NR1 (2a-c) (R = Ph, Me; R-1 = Me, i-Pr). Compounds 3 are stable in the solid state at 20 degrees C but rearrange in solution to 1-metalla-1,3,5-hexatrienes 7a-c by ring opening of the cyclobutene ring and subsequent 1,3 hydrogen migration. Compounds 3a and 7b were characterized by crystal structure analyses.

引用

页码：1197 / 1201

页数：5

共 19 条

[1]

AUMANN R, 1994, SYNLETT, P1041

[2]

AUMANN R, 1993, SYNLETT, P669

[3] ORGANIC SYNTHESES VIA TRANSITION-METAL COMPLEXES .51. 1-METALLA-1,3,5-TRIENES AND 1-METALLA-1,3-DIEN-5-YNES OF CHROMIUM AND TUNGSTEN BY INSERTION OF ALKYNES INTO M=C AND C=C BONDS OF 1-METALLA-1,3-DIENES AND 1-METALLA-1-EN-3-YNES, RESPECTIVELY [J].

AUMANN, R ;

HEINEN, H ;

HINTERDING, P ;

STRATER, N ;

KREBS, B .

CHEMISCHE BERICHTE, 1991, 124 (05) :1229-1236

[4] Dichotomy of enamines at the CC bond of a (1-alkynyl)carbene tungsten complex.: (1-azoniabutadien-4-yl)carbonylmetalates (-OC)5WC(OEt)=CR1C(=N+R2)Me, stable torsion isomers of (2-aminoethenyl)carbene complexes (OC)5W=C(OEt)CR1=C(NR2)Me [J].

Aumann, R ;

Roths, K ;

Frohlich, R .

ORGANOMETALLICS, 1997, 16 (26) :5893-5899

[5]

Aumann R, 1997, SYNLETT, P621

[6] Organic syntheses via transition metal complexes .86. Regioselective [C-3+C-2] cyclopentadiene annulation to enamines with alkynylcarbene complexes of chromium and tungsten as novel C-3 building blocks [J].

Aumann, R ;

Meyer, AG ;

Frohlich, R .

ORGANOMETALLICS, 1996, 15 (23) :5018-5027

[7] ORGANIC SYNTHESES VIA TRANSITION-METAL COMPLEXES .54. CYCLOPENTADIENES FROM 1-METALLA-1,3-DIENES AND ALKYNES BY CYCLIZATION OF INTERMEDIATE 1-METALLA-1,3,5-TRIENES (METAL = TUNGSTEN) [J].

AUMANN, R ;

HEINEN, H ;

DARTMANN, M ;

KREBS, B .

CHEMISCHE BERICHTE-RECUEIL, 1991, 124 (10) :2343-2347

[8] ORGANIC SYNTHESES VIA TRANSITION-METAL COMPLEXES .74. NOVEL PHOSPHONIUM ALLENIDE AND 2-PHOSPHANYLETHENYL CARBENE CHROMIUM AND TUNGSTEN COMPLEXES [J].

AUMANN, R ;

JASPER, B ;

LAGE, M ;

KREBS, B .

CHEMISCHE BERICHTE, 1994, 127 (12) :2475-2482

[9] Organic syntheses via transition metal complexes, XCI. Dihydropyridinyl carbene complexes by [4+2] annulation of alkenyl- or aryl imines to (1-alkynyl)carbene complexes of chromium and tungsten [J].

Aumann, R ;

Yu, ZK ;

Frohlich, R .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1997, 549 (1-2) :311-318

[10] 1-metalla-1,3,5,7-octatetraenes by 4-addition of (1,3-dien-2-yl)amines to (1-alkynyl)carbene complexes (M=Cr, W) [J].

Aumann, R ;

Göttker-Schnetmann, IJ ;

Wibbeling, B ;

Fröhlich, R .

TETRAHEDRON LETTERS, 1998, 39 (08) :795-798

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