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Expansion of Three-Membered Heterocycles to Five-Membered Cyclic CarbenesЧNovel Reactions of Aziridine Oxirane and Thiirane with CO and CS Ligands in Iron Ruthenium and Manganese Complexes.

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and eluted with water (0.02 mL min-'). The concentration
and degree of resolution of the enantiomers were measured by UV absorption and ORD spectroscopy (A=210700 nm).
The first group of compounds studied were acyclic (+)a-amino acids, such as alanine, serine, threonine, asparagine, and lysine. The total amount of every amino acid
loaded was recovered within the first 4 mL eluted. No optical activity was detected in the eluates (error limit 0.01
cm-', A=210-700 nm), i.e. these compounds were not
resolved to a measurable extent. When (+)-proline was
eluted, however, the eluates exhibited an ORD spectrum.
Amino acid analysis of the eluates indicated that they only
contained proline as a solute. Accordingly, neither decomposition of proline nor replacement of the ligand in the
rhodium complex occurred during elution. The molecular
rotation at 250 nm ([112]250) varied with the elution volume
from an initial negative value ( - 33 ") to a final positive
value (+34"). Since [m]250for (S)-proline is -880", it is
concluded that (S)-proline was eluted first with 3.8% followed by (R)-proline with 3.9% enantiomeric purity. These
Table I. Resolution on a A-Ru(phen):+ montmorillonite column [a].
[mli [bl
ee [%] [c]
I [nml
-33 (+34)
[3.8 (3.9)]
+390 ( - 1000)
112 (30)1
250 ( - 560)
119 (4311
+20 (-39)
[5 (2911
- 11 (+ 54)
16.8 (33)l
- 20 (+98)
L2.3 (12)l
2-piperidinecarboxylic acid
4-thiazolinecarboxylic acid
peridinecarboxylic acid, 3105-95-1 ; R-2-piperidinecarboxylicacid, 1723-008 ; ( f)-4-thiazolidinecarboxylic acid, 19291-02-2;S-4-thiazolidinecarboxylic
acid, 45521-09-3; R-4-thiazolidinecarboxylic acid, 34592-47-7; montmorillonite, 1318-93-0.
[I] P. E. Hare, E. Gil-Av, Science 204 (1979) 1226; V. A. Davankov, Yu. A.
Zolotarev, A. A. Kurganov, J. Liq, Chromatogr. 2 (1979) 1191; G.
Blaschke, Angew. Chem. 92 (1980) 14; Angew. Chem. Int. Ed. Engl. 19
(1980) 13; V. Schurig, R. Weber, J . Chromatogr. 217(1981) 51.
[2] A. Yamagishi, R. Ohnishi, M. Soma, Chem. Lett. 1982. 8 5 ; A. Yamagishi,
R. Ohnishi, J. Chromatogr. 245 (1982) 213; Inorg. Chem. 21 (1982)
Expansion of Three-Membered Heterocycles to FiveMembered Cyclic Carbenes-Novel Reactions of
Aziridine, Oxirane, and Thiirane with CO and CS
Ligands in Iron, Ruthenium, and Manganese
By Mono M . Singh and Robert J. Angelici*
Aziridine 1, oxirane 2, and thiirane 3 react with carbonylmetal complexes and undergo ring opening; initial
reaction is at the metal center^^^.'^]. So far, however, there
have been no reports of direct reactions of CO or CS ligands with 1, 2, or 3. We describe here some novel reactions of 1, 2, and 3 with these ligands in certain carbonylmetal compounds, yielding cyclic carbenes as the end
products. Thus, reaction of 1 with the metal complexes
and the ammonium bromide Br(CH,),NH:Br(molar ratio 1 : 1 : 1) in CH3CN affords the cyclic amino(oxy)carbenes 5a-d.
[a] Eluent: water. [b] Rotation values of the first and the last fractions are
shown without and in parenthesis, respectlvely. [c] Values in the square
brackets show the corresponding enantiomeric excess (ee).
values were improved to 14 and 16%, respectively, when
the fractions for V=0-3 mL and 3-7 mL were chromatographed again.
This success, together with the failure to resolve acyclic
a-amino acids, led us to attempt the resolution of other
kinds of cyclic organic compounds. Five of these (Table 1)
were successfully resolved, but five others (xylose, 2-methylpiperidine, 2-ethylpiperidine, 3-piperidinecarboxylic
acid, and a-acetyl butyrolactone) were not.
The present findings indicate that clay-metal chelate adducts are highly promising absorbents for the chromatographic resolution of enantiomeric mixtures of organic
compounds. In addition, the systems are interesting as
models for the propagation of chirality in nature during
chemical evolution. Indeed, clay modif3ed by optically active metal complexes could lead to the resolution of amino
Angew. Chem. Int. Ed. Engl. 22 (1983) No. 2
a, M=CpFe(CO)*; b, M=CpMn(CO)(NO); c, M=CpRu(CO),;
d , M=CpFe(CO)(PPh,); anions: PF;
5a-d are obtained as crystalline hexafluorophosphates
in 98%17],87Y0[~],
87%, and 70% yields, respectively, by extraction of the vacuum-dried residue with CH,C12 and precipitation with ether at - 20 "C. Several other halides, such
as Br(CH2)3NH:Br-, NaBr, (nBu),N+Br-, Et3NH+Brand (nBu),N+I- were also observed to catalyze the reaction of 1 with 4a. 5a is still obtained in 80% yield on decreasing the concentration of the Br(CH2),NH; Br- tenfold.
Similarly, reaction of 1 with the carbonyl(thiocarbony1)complex 6 in THF in the presence of Br- furnishes the
cyclic amino(thi0)carbene 7 in 83% yield.
Received: September 7, 1982; revised: November 19, 1982 [Z 144 IE]
German version: Angew. Chem. 95 (1983) 158
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1983, 140-147
CAS Registry numbers:
A-Ru(phen)$ +,24162-09-2; (?)-Proline, 609-36-9; S-Proline, 147-85-3; RProline, 344-25-2; (+)-5-Oxoproline, 149-87-1; R-5-Oxoproline, 4042-36-8;
S-5-Oxoproline, 98-79-3; (+)-5-MethyI-2-pyrrolidinone, 62182-32-5; S-5Methyl-2-pyrrolidinone, 1558-60-7; R-5-Methyl-2-pyrrolidinone, 21395-93-7 ;
(?)-y-Valerolactone, 57 129-69-8; R-y-Valerolactone, 58917-25-2; S-y-Valerolactone, 19041-15-7; (*)-2-piperidinecarboxylic acid, 4043-87-2: S-2-pi-
[*I Prof. Dr. R. J. Angelici, Dr. M. M. Singh
Department of Chemistry and Ames Laboratory U. S., DOE
Iowa State University, Ames, IA 50011 (USA)
[**I Ames Laboratory is operated for the U. S. Department of Energy by
Iowa State University under Contract No. W-7405-Eng-82. This research
was supported by the Office of Basic Energy Sciences, Chemical
Sciences Division.
0 Verlag Chemie GmbH, 6940 Weinheim. 1983
0570-0833/83/0202-0163 $ 02.50/0
Reaction of 2 in excess with 4a-d in the presence of
Br- in Br(CH2)zOH as solvent leads to formation of the
cyclic dioxycarbenes 10a-d in 81Y0[~~,
SOYO,73%, and 81%
yields, respectively. High yields (> 70%) of 10a, lob, and
10d are also obtained when Br(CHZ),0H is used instead of
4 a -d
Unlike 1 and 2, 3 does not react with 4a-d to form the
oxy(thio)carbene. However, it does form the dithiocarbene
13[Io1on reaction with 6 in presence of NaBr.
ganometallic compounds of elements of the transition series with actual tetrahedral structure are, as yet, unknown.
A plausible strategy for the synthesis of such compounds would be the use of Fe(CO)Z(NO)zas starting material, a member of the pseudo-Ni(CO), series in the sense
of the nitrosyl-shift principle[31. Replacement of a C O
group in Fe(CO)Z(NO)z by another two-electron ligand,
e.g. a phosphane, and of an NO group by another threeelectron ligand, e. g. an aryldiazenyl group, would result in
the Fe atom in the compounds Fe(CO)(NO)(NNR)PR, being a center of chirality. On using a pure phosphane enantiomer, e . g . one of the aminophosphanes (S)PPh,(N(R)CHMePh}151of Scheme 1, each complex is
formed in the form of two diastereomers a and b, which
differ only in the configuration at the Fe atom.
All the cyclic carbene compounds have been fully characterized as PF; salts by elemental analysis, and I R and
’H- and I3C-NMR spectral data. The formation of carbene
ligands has been conclusively proven by the I3C-NMR signals of the carbene carbon atoms [(CD,CN), 5a-d:
6=220.24, 228.56, 206.28, 234.20; 10a-d: 6=242.51,
253.43, 227.08, 254.00; 7 : 6=234.36; 13: 6=295.40].
Received: October 4, 1982 [ Z 166 IE]
revised: November 19, 1982
German version: Angew. Chem. 95 (1983) 160
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1983, 184-192
131 W. P. Giering, M. Rosenblum, J. Tancrede, J . Am. Chem. SOC.94 (1972)
7 170.
[4] b) W. Danzer, W. P. Fehlhammer, A. T. Liu, G. Thiel, W. Beck, Chem.
Ber. 115 (1982) 1682, and references cited therein.
171 H. Motschi, R. J. Angelici, Orgnnometnllics I (1982) 343.
[lo] F. B. McCormick, R. J. Angelici, Inorg. Chem. 20 (1980) 1 1 1 1 .
la, b
5a. b
7a, b
6a, b
Scheme 1
Optically Active Iron Complexes
with Tetrahedral Structure
By Henri Brunner* and Wolfgang Miehling
Most of the previously documented optically active organometallic compounds of the transition elements have
a n (arene)ML’L2L3-type structure[’]. These complexes are
designated as pseudotetrahedral, because the central metal
is bound to four ligands, and consequently only the isomeric “image” and “mirror image” tetrahedral structures
are possible. The geometry of these compounds is, however, octahedral with the 6 .n-arene ligand, frequently benzene or cyclopentadienyl, occupying three cis-positions of
the octahedron. This is born out, in particular, by the angles between the ligands L’, Lz and L3 to the metal atom,
which are always approximately 9OoLZ1.
Optically active or[*] Prof. Dr. H. Brunner, W. Miehling
Institut fur Anorganische Chemie der Universitat
Universitatsstrasse 31, D-8400 Regensburg (Germany)
Optically Active Transition Metal Complexes, Part 82. This work was
supported by the Deutsche Forschungsgemeinschaft, the Fonds der
Chemischen Industrie, and BASF AG, Ludwigshafen.-Part 81: I. Bernal, W. H. Ries, H. Brunner, D. K. Rastogi, Inorg. Chem., in press.
0 Verlag Chemie GmbH, 6940 Weinheim, 1983
The anion Fe(CO),(NO)- reacts with diazonium ions
arylNN+ in acetone at -78 “C to give the complex
Fe(CO),(NO)(NNaryl), which is unstable at room temperatureL6].However, if one equivalent of aminophosphane is
added at - 78 “C, further exchange of C O takes place with
formation of the complexes 1-7 (Scheme l), which can be
isolated in 40-65% yield after warming to room temperature: 1 and 2 as readily decomposable red oils, 3-7 as
stable reddish-brown powders.
The IR spectra of the complexes 1-7 in pentane solution each show sharp, very intense bands for vco (19751980), vN0 (1730-1735) and vNN(1662-1682 cm-’). The
diastereomers a and b of complexes 3, 4, and 6 d o not
differ in their ’H-NMR spectra. In the case of compounds
3 and 4 substituted in the p-position or without substituents on the diazoaryl moiety this is not surprising, but is,
however, for the complex 6 which has phenyl substituents
o n the o-position. Only the compounds 5 and 7, substituted by methyl in the o-positions, showed different chemical shifts in the o - C H ~signals [6=2.22 (7a) and 2.28 (7b),
C&], the C*CH,, and the NCH3 signals, from which the
diastereomeric ratio a : b can be determined.
None of the diastereomers of complexes 3-7 can be enriched by fractional crystallization. In contrast, the diastereomeric pairs Of 4,
and can be separated by preparative liquid chromatography on Merck-Lobar B-columns.
0570-0833/83/0202-0164 $02.50/0
Angew. Chem. Int. Ed. Engl. 22 (1983) No. 2
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