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dried in vacuo with toluene twice to remove any remaining solvent and water. The
dried resin was weighed and used in the screening procedure. The resin-supported
Isomers of the Elemental Composition CN,O
ligand (0.02 mmol) was placed in a dried test tube with a rubber septum under an Giinther Maier,* Hans Peter Reisenauer,
argon atmosphere. Ti(OiPr), (0.1 M in toluene, 200 pL, 0.02 mmol) was added and
allowed to stand for 1 h. Subsequently, cyclohexene oxide ( 1 . 0 ~in toluene, 200 pL,
Jiirgen Eckwert, Matthias Naumann, and
0.2 mmol) and TMSCN ( 1 . 0 ~In toluene 200 pL, 0.2 mmol) were added, and the Michael De Marco
reaction was gently agitated for 20 h (4 “C). The reaction was quenched by addition
of Et,O ( I .O mL), and the solution forced through a silica gel plug with additional In our search for the still unknown molecule C2OZ,[l1we
Et,O (1.0 mL). Reaction selectivity was determined by GLC analysis (BE-
TADEX 120 chiral column).
irradiated cyanogen di-N-oxide (1) in solid argon at 10 K with
light of wavelength 254 nm. Nitrosyl cyanide (3) was formed,
Received: March 5, 1997 [Z10201IE] probably by loss of CO from the rearrangement product 2.[’,31
German version: Angen,. Chem. 1997, 109, 1781-1785
OeNEC-CZN+O O=C=N-CEN+O

Keywords: asymmetric catalysis epoxides - heterogeneous 1 2

catalysis peptides * solid-phase synthesis
When an ArF laser (2 = 193 nm) was used, a new species with a
strong IR absorption at 1837 cm-’ was generated instead of 3.
[l] B. M. Cole, K. D. Shimizu, C. A. Krueger, J. P. A. Harrity, M. L. Snapper, Since the position of this band could be reasonable for C202,[41
A. H. Hoveyda, Angen. Chem. 1996,108, 1776-1779; Angew. Chem. Int. Ed. we attempted to determine its origin. A more precise study of the
Engl. 1996, 35, 1668-1671. photochemistry of 3 in an argon matrix at 15 K showed that the
[2] Recent advances in the application of combmatorial techniques in the discov-
ery of chiral catalysts: a) F M. Menger, A. V. Eliseev, V. A. Migulin, J. Org.
above-mentioned absorption is not due to C,O, but to isonitro-
Chem. 1995. 60. 6666-6667; b) G. Lin, J. A. Ellman, ibid. 1995, 60, 7712- syl cyanide (5). To the best of our knowledge this isomer of 3 is
7713: c) S. R Gilbertson, X. Wang, Tetrahedron Lett. 1996, 37, 6475-6478; the first “organic” isonitrosyl compound.151
d) K. Burgess, H. Lim, A. M. Porte, G. Sulikowski, Angew. Chem. 1996, 108, Four ways of linking an NO group and a CN moiety are
192-194; Angelic Chem. Inr. Ed. Engl. 19%,35, 220-222.
[3] F. Balkenhohl, C. von dem Bussche-Hunnefeld, A. Lansky, C. Zechel, Angew conceivable: not only 3, which was synthesized in 1971,[61but
Chem. 1996, /OH, 2436-2487; Angen. Chem. Int. Ed. Engl. 1996, 35, 2288- also nitrosyl isocyanide (4), isonitrosyl cyanide (5), and isonitro-
2337 syl isocyanide (6) are minima on the C N 2 0 energy hypersur-
[4] a ) H. Nitta, D. Yu, M. Kudo, A. Mori, S . Inoue, J. Am. Chem. Soc. 1992, f 14, faceL7].Their relative energies and structural data, calculated
7969~7975, and references therein; b) M. Hayashi, Y. Miyamoto, T Inoue, N
Ogunt, J Org. Chrm. 1993, 58, 1515-1522.
with the density functional theory (DFT) method BLYP/6-
[5] Although the synthesis of all peptide combinations is straightforward, we are 31 1+G*18’in the Gaussian 94 package of programs,191are given
currently limited in our ability to evaluate efticiently every possible ligand for in Scheme 1. This DFT method was chosen because MP2 cal-
asymmetric induction. Studies aimed at developing strategies that address this
issue are under way.
[61 C. T. Dooley, R A Houghten, Life Sciences 1993, 52, 1509-1517.
Our initial efforts towards carrying out ligand screening on a solid support A E I kcal rno1-I
were unsuccessful [l]
R. Noyori, A.svmmetric Cotalysrs in Orgunic Chemrstry, Wiley, New York, - 49.2 O=N. .C--N 7
1994, pp. 346- 364.
- 34.1 N---O--N=C 6
Although levels of selectivity on solid and in solution phases may correlate,
they may not he reliable. This is particularly an issue if selectivites on solid - 31.1 N U C E N 5
phases are low (for example less than 15% ee). In such instances ranking of
various catalyst systems in order of their effectiveness becomes increasingly - 15.9 - N 4 < 4
dubious. since differences in selectivity are small.
- 0 W - C r N 3
An initial analysis of various solvents (toluene, CH,CI,, T H E Et,O, and
MeCN) indicated that the most selective and reproducible results were ob-
tained in toluene.
C Bolm in Adiunced Asj.mmetric Synthesis (Ed.: G. R. Stephenson), Blackie
Academic and Professional, London, 1996, pp. 9-26.
The predicted nonlinear effect, based on the model in which homo- and het-
erodimers of the catalyst are present but dissociate at different rates to give the
active monomeric catalyst, is calculated with Equation (a). (ee,,,[%] =
ee,,isd = [ee,., x ( K x e e , J / [ K x eel,,+ 1 x (I00 - eel,,)] (2)
3 ‘a
entiomeric excess of the product with optically pure ligand, ee,,,rh] =
enantiomeric excess of the ligand, K = ratio ofthe initial rates ofoptically pure
versus racemic ligands ( K = 3 in this case)): K. Mikami, M. Terrada, Tetrahe- N 179.5’ I 189
dron 1992, 48, 5671 -5680
A. Akelah. D. C. Sherrington, Chem. Rev. 1981,8f, 557-587.
All reaction products i n Table 3 were fully characterized by ’H, I3C NMR, and
IR spectrometry, high-resolution mass spectroscopy, or combustion analysis. 5 6
The effect of the glycine at AA3 was originally not appreciated and therefore
went unnoted [ l ] (I 172) (I151)
FMOC-Gly-PAC resin (PerSeptive Biosystems; FMOC = 9-fluorenylmethy-
loxycarbonyl) may also be used to obtain similar results.
1.179
N-C - 1.16
* N-0

7
Scheme 1. Calculated relative energies and geometries (BLYP/6- 31 1 +GI) of the
CN,O isomers 3-6and the radical pair 7(distances in A). All CN,O isomers possess
C, symmetry. Experimental data are given in parentheses [6b, 1 I ]

[*] Prof. Dr. G. Maier, Dr. H. P. Reisenauer, Dr. J. Eckwert,

Dip].-Chem. M. Naumann, DipLChem. M. De Marco
Institut fur Organische Chemie der Universitat
Heinrich-Buff-Ring 58, D-35392 Giessen (Germany)
Fax: Int. code +(641)99-34309

Angew. Chem. Int Ed Engl. 1997, 36, No. 16 0 WILEY-VCH Verlag GmhH, D-69451 Weinheim, 1997 0570-0833/97/3616-1707 $17 50+ 5010 1707
COMMUNICATIONS
culations give less accurate results, especially for NO' and Table 1. Calculated vibrational spectrum of 3 (BLYP/6-311+ G*) and experimen-
CN'.[''I According to the energy scheme, 4 should be even tally observed IR absorptions (Ar matrix, 15 K ; relative intensities are given in
parentheses)
more easily accessible than 5. Indeed, this species can also be
generated and identified by matrix spectroscopy if 3 is irradi- Type [dl v,,I,d/cm- ?exJ cm-I
ated with light of wavelengths greater than 570 nm instead of
193 nm. v1 A CN str 2126 (25.0) 2163.0 (60.2)
13C: 2079 13C: 2113.4
v2 A NO str 1469 (100.0) [b] 1498.5 (100.0)
13C: 1468 I3C: 1497.3
I5N: 1443 15N: 1472.5
'*O: 1430 " 0 : 1460.2
vj A ip 748 (31.0) 809.5 (64.8)
1JC: 738 13C: 798.6
s4 A ONC str 573 (29.0) 576.1 (26.6)
13C: 567 13C: 5709
vb A oop 212 (10.0)
N--O--C3N s5 A ip 199 (8.0)
5
[a] str = stretching vibration; ip = in-plane bending vibration; oop = out-of-plane
bending vibration. [b] Absolute intensity 141 kmmol-'.

Isomers 3, 4, and 5 are probably linked to each other by the

radical pair 7.However, this intermediate could not be detected, Table 2. Calculated vibrational spectrum of 4 (BLYP/6-311 +G*) and experimen-
presumably because it is trapped in the matrix cage and tally observed IR absorptions (Ar matrix, 18 K ; relative intensities are given in
parentheses).
undergoes immediate recombination. In any case, all three iso-
mers can be interconverted photochemically; the relative ratios Type [a1 a,,,,,/c1n- Gcxp/ cm-'
of the components were determined by the different UV/Vis
absorptions (3: Figure lc, 4: Figure Ib, 5: Figure la). Com- i', A CN str 1944 (9.0) 1997.5 (26.1) [b]
13C: 1913 1967.1 (33.1)
[1978.5]
"C: 1945.9
a s2 A NO str 1795 (100.0) [c] 1681.0 (100.0)
I3C: 1786 "C: 1677.2
v, A ip 650 (11.0) 723.4 (21.7)
"C: 649 "C: 723.4
v4 A N N str 284 (19.0) 261.0 (40.5)
1%: 282 "C: 259.0
s5 A ip 163 (0.4)
Vb A oop 31 (0.0)
Combination bands and overtones (probable assignment): 3312.2 (Zv,), 2415.1
b
(s2 +
Vj), 974.4 (v, +
v4), 539.8 (2v,)
3.03 [a] See footnote [a] of ydbk 1. [b] Anharmonic resonance of sI with the combina-
i O=N-N=C 4 +
tion mode (s, v4). The hand position of the fundamental tone (in parentheses) was
determined from the resulting bands and their relative intensities [c] Absolute
intensity 823 kmmol-'.

Table 3. Calculated vibratlonal spectrum of 5 (BLYP/6-311 +G*) and experimen-

tally observed IR absorptions (Ar matrix, 1 5 K ; relatlve intensities are given in
C parentheses).

OzN-CEN 3 Type [a1 ~,,,,d/cm- cm-'

iexD/

v, A C N str 2079 (1.3) 2086.0 (0.6)

" C : 2034 "C: 2043.5
v2 A NO str 1939 (100.0) [b] 1836.9 (100.0)
13C: 1939 "C: 1836.9
"N: 1904 I5N: 1804.9
01 I I i I l I I T I " 0 : 1888 " 0 : 1789.2
300 400 500 600 700 sj A ip 469 (1 3 ) 488.4 (1.2)
linm + 13C: 466 "C: 482.5
sq A CO str 243 (4.2)
Figure 1. Experimental UV spectra of the two new isomers 5 (a) and 4 (b) as well S6 A oop 11 1 (0.05)
as the starting material 3 (c) in an Ar matrix at 15 K . v5 A ip 92 (0.05)
Combination bands and overtones (probable assignment): 3650.7 (2v,), 2313 0
( V 2 + va)

pound 3 is the preferred isomer at excitation with light of wave- [a] See footnote [a] of Table I . [b] Absolute intensity 632 kmrnol-'
length 1= 254 or 405 nm, 4 at 1> 570 nm, and 5 at I = 185 or
193 nm. No IR bands attributable to the fourth isomer 6 were
detected. bands in the accessible spectral range (C > 220 cm- '). Three
For the planar molecules 3,4, and 5 (C,symmetry), six IR-ac- of these-namely, the N-N stretching vibration at 261.0 cm-',
tive fundamental vibrations of varying intensity are expected a bending mode at 723.4cm-', and the N - 0 stretching
(Tables 1-3). According to the calculation 4 should exhibit four vibration at 1681.0 cm-' (Figure 2b)-are readily assigned by

1708 0 WILEY-VCH Verlag CrnbH, D-69451 Weinheim, 1997 0570-0833/97/3616-1708 $17.50+.80/0 Angew Chem. Int. Ed. Engl. 1997, 36, No. 16
 COMMUNICATIONS
comparison with the theoretical predictions. Instead of a single [l] G. Maier, H. P. Reisenauer, B. Rother, J. Eckwert, Liebig.\ Ann. 1996, 303-
absorption for the C-N stretching mode (v,) we observe a pair 306, and references therein.
[21 G. Maier, J. H. Teles, Angew. Chem. 1987, 99, 152-153; Angrit-. Chem. Int. Ed.
of bands at 1997.5 and 1967.1 cm-', which arise from anhar- Engl 1987,26,155-156.
monic resonance with the combination mode v z + v4. This inter- [3] G. Maier, M. Naumann, H. P. Reisenauer, J. Eckwert, A n g w Chem. I%,
pretation was unequivocally confirmed by a '3C-labeling exper- 108, 1800-1801; Anget. Chem. Int. Ed. Engl. 1996,35, 1696.1697.
iment. Due to the resulting band shifts, the accidental [4] Review: J. A. Berson, D. M. Birney, W. P. Dailey, 111, J. F. Liebman in Molec-
ular StrucrureandEnergetics, Vol. 6(Eds.: J. F. Liebman, A. Greenberg), VCH,
degeneracy of the fundamental and combination modes is re- New York, 1988, pp. 391 -441.
moved, and only the band for the I3C-N stretch appears at [5] The reaction of F atoms with NO leads to both possible isomers, ONF and the
1945.9 cm-'. "inorganic" isonitrosyl compound NOF. The latter yields the thermodynami-
cally more stable nitrosyl isomer upon irradiation in a matrix at 8 K: R. R.
Smardzewski, W. B. Fox, J Chem Soc. Chem. Commun. 1974, 241 -242; J.
Chem. Phys 1974,60,2104-2110.
2 9 v2
a [6] a) P. Horsewood, G. W. Kirby, J. Chem. Suc. Chem. Cummrm. 1971, 1139-
I 1140; b) R. Dickinson, G. W. Kirby, J. G. Sweeny, J. K. Tyler, rbid. 1973.
I I N-0-CZN 5 241-242; c) E. A. Dorko, L. Buelow, J. Chem. Phys. 1975,62, 1869-1872.
[7] a) A. A. Korkin, P. von R. Schleyer, R. J. Boyd, Chem. P h p Lett. 1994,227,
312-320: b) B. G. Gowenlock, L. Radom, Ausr J Chrm 1978, 31, 2349-
2353.
[8] Review: L. J. Bartolotti. U. Flurchick, Rev. Comput. Chem. 1996, 7, 187 -216.
"1 x40
[9] Gaussian 94, revision B.1: M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W.
Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A.Petersson,
J. A. Montgomery, K. Raghavdchari, M. A. Alaham, V. G. Zakrzewski,
b J. V.Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M.
Challacombe, C. Y Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres,
O=N-N=C 4 E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J.
Derees, J. Baker, .I. P. Stewart, M. Head-Gordon, C. Gonzalez, J. A. Pople.

A
t v4
Gaussian Inc., Pittsburgh, PA, USA, 1995.
[lo] a) B. G. Johnson, P. M. W. Gill, J. A. Pople, J. Chem. Pliys. 1993, 98, 5612-
5626; b) own calculations with the Gaussian 94 program MP2/6-311 + G*.
[I 11 G. Herzberg, Specrra of Diatomic Molecules, Van Nostrand, Princeton, 1950
v3
I [12] ONCl ( N - 0 stretching vibration: 3 ~ 1 8 0 cm-')
5 isomerizes to NOCl ( N - 0
0a stretching vibration' i = 1842 cm-') upon irradiation at i = 193 nm. The re-
C verse reaction is initiated with light of wavelength i.2310 nm M. De Marco,
I
Diplomarbeit, Unwersitiit Giessen, Germany, 19%.
O=N-CrN 3

2,3-Dihydrothiazol-2-ylidene
2000
- :500

c /cm-'
to00 500

Figure 2. Experimental IR spectra of the two new isomers 5 (a) and 4 (b) as well as
Gunther Maier,* Jorg Endres, and
Hans Peter Reisenauer
the starting material 3 (c) in an Ar matrix at 15 K. Dedicated to Professor Peter Welzel
on the occasion of his 60th birthday

The analysis of the IR spectrum of 5 (Figure 2a) is less prob- There are two main approaches for investigating species that
lematic. The most intense band by far is that due to N - 0 are not isolable under normal conditions : increasing their kinet-
stretching (v,) at 1836.9 cm-', the first overtone of which ap- ic stability by introducing sterically demanding substituents and
pears at 3650.7 cm-'. The C-N stretching vibration gives rise utilizing matrix-isolation techniques. The first method was suc-
to a weak absorption at 2086.0 cm-'; the equally weak band at cessfully applied to nucleophilic carbenes by Arduengo
485.4 cm- ' is due to a bending mode. We have not yet been able et al.['"*'"] However, it later turned out that, at least for the
to definitively assign an experimental absorption to the C - 0 imidazolylidenes, steric hindrance is of secondary impor-
stretching transition, which should occur at the lower end of the tance.['b] The second method, which should be suitable for de-
accessible spectral range. tecting unsubstituted parent compounds and allows a compari-
Two further computational results worth mentioning are the son of the experimental data with quantum-chemical
long N - N bond in 4 (1.72 A; typical N-N single bonds are calculations, was not employed for this class of compounds until
1.4 A) and the long 0 - C bond in 5 (2.21 A; typical C - 0 single now.
bonds are 1.4-1.5 A). 2,3-Dihydrothiazol-2-ylidene(2) was selected as the target
It must be assumed that the conversion of 3 into an isonitrosyl molecule for several reasons. This ring system exemplifies the
isomer is not unique, but may also occur with other nitrosyl nucleophilic carbene, since, as Breslow showed almost 40 years
species. This is supported by the corresponding rearrangement ago,['] it is the structural element that is responsible for the
in nitrosyl 'I activity of vitamin B, .[31 Additionally, the catalytic activity of
the thiazolium salt/2 system is of technical interest.[41During the
Received: January 23, 1997 [Z10027IE] recent renaissance of nucleophilic carbenesI5] 2,3-dihydro-
German version: Angew,. Chem. 1997, 109, 1785-1787
[*] Prof. Dr. G. Maier, DipLChem. J. Endres, Dr. H. P. Reisenauer
Institut fur Organische Chemie der Universitat
Keywords: ab initio calculations * isomerizations . matrix isola- Heinrich-Buff-Ring 58, D-35392 Giessen (Germany)
tion - photochemistry * radicals Fax: Int. code +(641)99-34309

Angew. Chrm. In8 Ed. Engi. 1997, 36, N o . 16 0 WILEY-VCH Verlag GmbH, D-69451 Weinhelm, 1997 0570-0833/97/3616-1709S 17.50+.50,0 1709