A novel electrophilic diamination reaction of alkenes

Article abstract of DOI:10.1002/1521-3773(20011119)40:22<4277::AID-ANIE4277>3.0.CO;2-I

A three-component electrophilic reaction transforms olefins into imidazoline and diamine derivatives (see scheme). Rhodium(II) heptafluorobutyrate dimer (2 mol%) was utilized as the catalyst and N,N-dichloro-p-toluenesulfonamide (TsNCl₂) and ac

Full text of DOI:10.1002/1521-3773(20011119)40:22<4277::AID-ANIE4277>3.0.CO;2-I

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[9] a) M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron
Lett. 1999, 40, 2247 ± 2250; b) J. P. Huang, E. D. Stevens, S. P. Nolan,
J. L. Petersen, J. Am. Chem. Soc. 1999, 121, 2674 ± 2678.
[10] M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953 ±
956.
[11] For a recent account on the reactivity of various imidazolylidene-
substituted Ru-complexes in the ring-closing olefin metathesis and
enyne metathesis, see: A. Fürstner, L. Ackermann, B. Gabor, R.
Goddard, C. W. Lehmann, R. Mynott, F. Stelzer, O. R. Thiel, Chem.
Eur. J. 2001, 7, 3236 ± 3253.
several new eletrophilic addition reactions, aminohalogena-
tion, and a,b-differentiated diamination reactions by using N-
halogenosulfonamides as the electrophiles.[6, 7] The regio- and
stereochemical features of the resulting haloamine and
diamine products have unambiguously proven the formation
of N-(p-tosyl),N-haloaziridinium or N-(o-nosyl),N-haloaziri-
dinium species during the reaction processes. In our continu-
ing research on this topic we have now discovered a novel
three-component reaction (Scheme 1) which provides access
to imidazolines[8] and a,b-diamino derivatives.[9, 10]
[12] Alkyne
9 was prepared by alkylation of ethoxyacetylene with
5-bromo-1-pentene (nBuLi, THF, 788C; 76% yield).
[13] For preparation of alkynyl phosphates, see: a) P. J. Stang, Acc. Chem.
Res. 1991, 24, 304 ± 310; b) V. V. Zhdankin, P. J. Stang, Tetrahedron
Lett. 1993, 34, 1461 ± 1462.
[14] For an alternative synthesis of 22, see: L. A. Paquette, G. J. Wells,
K. A. Horn, T.-H. Yan, Tetrahedron 1983, 39, 913 ± 924.
[15] DFT calculations (pBP/DN*; MacSpartan Pro 1.0.2) indicated that
1
diene 3 was 44 kcalmol lower in energy than the starting enyne
precursor 2.
[16] Previously, depending on the substitution pattern of the enyne
precursor, either pathway I[16b,c] or pathway II[16a,d] were postulated
to operate: a) A. Kinoshita, M. Mori, Synlett 1994, 1020 ± 1022; b) S.-
H. Kim, W. J. Zuercher, N. B. Bowden, R. H. Grubbs, J. Org. Chem.
1996, 61, 1073 ± 1081; c) T. R. Hoye, S. M. Donaldson, T. J. Vos, Org.
Lett. 1999, 1, 277 ± 279; d) T. Kitamura, Y. Sato, M. Mori, Chem.
Commun. 2001, 1258 ± 1259.
[17] This outcome is fully consistent with prior results reported by Grubbs
and co-workers: P. Schwab, R. H. Grubbs, J. W. Ziller, J. Am. Chem.
Soc. 1996, 118, 100 ± 110.
Scheme 1. Chalcone-based electrophilic diamination reaction.
The current study was initiated by attempts to render the
parent version of the aminohalogenation reaction asymmetric
and catalytic.[6] Unfortunately, the success of this effort has
been seriously limited thus far. For most of the cases we
examined the reaction was either significantly deactivated or
poor enantiomeric excesses resulted when chiral amine
ligands were employed together with copper or zinc ions.
Therefore, the search for other metal alternatives or metal ±
ligand complexes became necessary. When rhodium com-
pounds were examined[11] (for example, rhodium(ii) acetate
dimer, rhodium(ii) trifluoroacetate dimer, and rhodium(ii)
heptafluorobutyrate dimer) the reaction of methyl cinnamate
with TsNCl2 (Ts ˆ tosyl ˆ toluene-4-sulfonyl) led to the for-
mation of complexes and a major side product. This side
product was isolated in a yield varying between 18 ± 25%
when the above catalysts were employed, although the
haloamine product was generated predominantly. The sub-
sequent X-ray structural analysis revealed that this new side
product is essentially a multifuctionalized imidazoline deriv-
ative (Figure 1).
A Novel Electrophilic Diamination Reaction of
Alkenes**
Guigen Li,* Han-Xun Wei, Sun Hee Kim, and
Michael D. Carducci
Electrophilic addition reactions of olefins have been of
fundamental importance in organic chemistry[1] because these
reactions can convert inexpensive petroleum alkenes into
chemically and biologically useful compounds. At present,
olefinic additions involving three or more components in a
single operation are rare,[2, 3] which is probably because of the
fact that only a few electrophilic addition intermediates
enable multistep transformations.[4, 5] Recently, we developed
[*] Prof. Dr. G. Li, Dr. H.-X. Wei, S. H. Kim
Department of Chemistry and Biochemistry
Texas Tech University, Lubbock, TX 79409-1061 (USA)
Fax : (‡1)806) 742-1289
E-mail: qeggl@ttu.edu
Dr. M. D. Carducci[‡]
Department of Chemistry
University of Arizona, Tucson, AZ 85721 (USA)
‡
[ ] To whom X-ray analysis data should be addressed.
[**] We gratefully acknowledge the National Institutes of Health (GM-
R15-60261), the Robert A. Welch Foundation (D-1361) for their
generous support, and the National Science Foundation for their
partial support of the NMR facility. We thank Mr. Subramanian Karur
and Mr. Jason D. Hook for their assistance. The preliminary results of
this work have been presented at the 221st ACS National Meeting,
San Diego, CA, April 2001.
Figure 1. X-ray structure of 1-p-toluenesulfonyl-2-dichloromethyl-4-phe-
nyl-5-methyloxycarbonylimidazoline.
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Encouraged by the importance of imidazolines and their
imidazole derivatives, as well as diamino acids, for biomedical
research,[8±10] we sought to make this side reaction the main
reaciton. Of the above rhodium compounds the rhodium(ii)
heptafluorobutyrate dimer proved to be the catalyst which
best favored formation of the imidazoline, and was thus
chosen as the lead candidate for examining the effects of the
reaction conditions. The model reaction was again based on
the use of methyl cinnamate as the substrate (entry 5 of
Table 1). Molecular sieves (4 Š) were initially found to
increase the formation of imidazolines, as revealed by crude
1H NMR spectroscopic analysis or thin-layer chromatography.
In fact, the yield of the imidazoline product increased to
nearly 35% in the presence of 4-Š molecular sieves. Next, our
attention was turned to employing ligands that would
coordinate with the rhodium(ii) center so as to change the
catalytic reactivity of the rhodium(ii) heptafluorobutyrate
dimer. It was found that the Ph3P ± rhodium(ii) complex
generated by treating 2.0 mol% of the rhodium(ii) hepta-
fluorobutyrate dimer with 4.0 mol% of triphenylphosphane
can completely inhibit the formation of haloamines. Con-
currently, the yield of the imidazoline product rose to
45%, and then to 51% when the N,N-dichloro-p-toluene-
sulfonamide was added to the reaction system in two
portions.[12]
Similar to our previous aminohalogenation systems, this
reaction is also very easy to perform. Essentially, it can be
conducted at room temperature in any convenient vessel of
appropriate size, without the need of inert atmosphere
protection. Although a,b-unsaturated esters were initially
utilized and resulted in successful examples, most of these
substrates did not perform as well as the a,b-unsaturated
ketones in this system as shown by the low yields (45% ±
51%) realized (entries 5 ± 7). Only in the aliphatic ester case
(entry 8) was a good yield (69%) obtained. However, the
yields and selectivities were improved when a,b-unsaturated
ketones were used as the substrates. Both aromatic and
aliphatic ketones worked well (66 ± 82% for entries 1 ± 4).
Interestingly, the terminal disubstituted substrates (entries 4
and 8) resulted in the highest yields (82 and 69%, respec-
tively) for both ketone and ester substrate categories. No
minor regioisomers were observed in the eight cases exam-
Table 1. PPh3-[{(C3F7CO2)2Rh}2]-catalyzed cyclic diamination.
Entry
1
Substrates
Product (Æ)
m.p. [8C]
Stereoselectivty
(anti:syn)[a]
yield [%][b]
130 ± 131
26:1
40:1
50:1
66
2
3
58 ± 59
oil
68
66
4
oil
±
82
5
6
7
126 ± 127
102 ± 104
oil
20:1
25:1
25:1
51
49
45
8
134 ± 136
±
69
1
[a] Estimated by crude H NMR determination. [b] Yields after purification by column chromatography.
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ined. The diastereoselectivity is good to excellent (syn:anti ˆ
20:1 ± 50:1).
The reaction rate, the yield, and stereochemical outcomes are
almost the same as those obtained under normal conditions.
The careful analysis of the resulting products also revealed
that no chlorination occurs at the 4- and/or 5-positions of the
imidazoline ring, hence a possible radical pathway can be
ruled out.
Our current investigation has been extended to examine the
hydrolysis of 1-p-toluenesulfonyl-2-dichloromethyl-4-phenyl-
5-methyloxycarbonylimidazoline by treating it with a 6n HCl
solution in THF to give the a,b-differentiated diamino ester
syn-methyl Na-(4-Ts),Nb-dichloroacetyl diaminophenylpropi-
onate (Scheme 3). Other synthetic properties, such as the
functionalization of the CHCl2 group and olefination to give
4,5-multifunctionalized imidazoles, will be studied in the
future.
Scheme 2 outlines the mechanistic proposal for the reac-
tion. The first step is the electrophilic addition to form the N-
(p-tosyl),N-chloroaziridinium intermediate (A).[13, 14] Rhodi-
um, as well as zinc and copper, can catalyze this trans-
formation. The Ritter-type nucleophilic attack by MeCN that
Scheme 3. Transformation of imidazoline to a,b-differentiated diamine.
Experimental Section
Triphenylphosphane (5.60 mg, 0.021 mmol), rhodium(ii) heptafluorobuty-
rate dimer (10.9 mg, 0.010 mmol), and freshly distilled acetonitrile
(2.50 mL) were added into a dry vial. The mixture was stirred at room
temperature for 40 min before 4-Š molecular sieves (200 mg, predried in
the oven at 2008C overnight) were added. The resulting mixture was stirred
for 10 min and loaded with chalcone (106 mg, 0.50 mmol; entry 1 of
Table 1) and the first portion of N,N-dichloro-p-tolunesulfonamide (60 mg,
0.25 mmol). Stirring was continued for 4 h at RT and followed by the
addition of the second portion of N,N-dichloro-p-toluenesulfonamide
(240 mg, 1.0 mmol). The resulting light yellow slurry was stirred at RT for
40 h in the capped vial without argon protection. The 4-Š molecular sieves
and other solid precipitates were filtered off and washed with EtOAc (3 Â
5 mL). The organic solution was directly concentrated without quenching,
purified by flash chromatography (with hexane and EtOAc (v/v ˆ 5/1) as
the eluent) to give 1 (0.162 g, 66%) as a colorless solid. m.p. 130 ± 1318C.
1H NMR (300 MHZ, CDCl3): d ˆ 7.80 ± 7.74 (m, 4H), 7.64 ± 7.61 (m, 1H),
7.49 ± 7.44 (m, 2H), 7.32 ± 7.23 (m, 6H), 6.90 (dd, J ˆ 1.4, 8.0 Hz, 2H), 5.56
(d, J ˆ 4.9 Hz, 1H), 5.01 (d, J ˆ 4.9 Hz, 1H), 2.45 (s, 3H); 13C NMR
(75 MHz, CDCl3): d ˆ 193.3, 156.7, 145.7, 138.7, 134.4, 134.3, 133.5, 130.1,
129.0(2), 128.8, 128.7, 128.0, 126.6, 72.3, 71.9, 61.4, 21.7; HR-MS (matrix-
Scheme 2. Possible mechanism of diamination.
effects ring opening gives nitrilium intermediate (B). Since
the anti configuration of methyl cinnamate is retained in the
product, the opening of the aziridinium ring by acetonitrile
clearly proceeds in a syn manner. It seems that the coordi-
nation of MeCN to the rhodium center occurs prior to the
aziridinium ring opening. The Lewis basic moieties used in
this coordination could be either the N-chlorine atom or the
sulfonyl oxygen atom of the Ts group. The cyclization of
intermediate B gives rise to the 1N-(p-tosyl),1N-chloroimi-
dazolinium C, which then undergoes a 1,3-displacement of the
1N-chlorine atom to give 1N-(p-tosyl),3N-chloroimidazolini-
um D. Deprotonation of the 2-methyl group of D gives the
methylene scaffold E, which enables the second SN2'-type
displacement to afford F. Chlorination of the 3N site of
intermediate F, which gives rise to G, is followed by the second
deprotonation of the 2-methyl group to yield H. At the final
step, the third 1,3-displacement of chlorine results in 1-p-
toluenesulfonyl-2-dichloromethyl-4-phenyl-5-methyloxycar-
bonylimidazoline.
‡
assisted laser desorption/ionization (MALDI) FT-MS): m/z [M ‡1] found:
487.0644, calcd for C24H20O3N2SCl2: 487.0644.
2: 1H NMR (300 MHz, CDCl3): d ˆ 7.78 (d, J ˆ 8.6 Hz, 2H), 7.74 (d, J ˆ
8.8 Hz, 2H), 7.22 (s, 1H), 6.92 (dd, J ˆ 2.0, 6.8 Hz, 4H), 5.53 (d, J ˆ 5.0 Hz,
1H), 5.01 (d, J ˆ 5.0 Hz, 1H), 3.88 (s, 3H), 2.45 (s, 3H); 13C NMR (75 MHz,
CDCl3): d ˆ 191.7, 164.5, 156.7, 145.6, 138.8, 134.5, 131.2, 130.0, 129.0, 128.6,
128.0, 126.6, 126.4, 114.2, 72.6, 71.5, 61.5, 55.6, 21.7; HR-MS (MALDI-
‡
FTMS): m/z [M ‡1] found: 517.0768, calcd for C25H22O4N2SCl2: 517.0750.
1
3: H NMR (300 MHz, CDCl3): d ˆ 7.55 (d, J ˆ 8.4 Hz, 2H), 7.32 (s, 1H),
7.18 ± 7.14 (m, 3H), 7.10 ± 7.08 (m, 2H), 6.69 (d, J ˆ 8.4 Hz, 2H), 5.14 (d, J ˆ
4.3 Hz, 1H), 4.28 (d, J ˆ 4.3 Hz, 1H), 2.40 (s, 3H), 2.39 (s, 3H); 13C NMR
(75 MHz, CDCl3) d 206.0, 156.8, 146.0, 139.6, 132.6, 130.3, 128.6, 127.5,
127.4, 125.6, 75.5, 71.5, 61.8, 26.6, 21.6; HR-MS (MALDI-FTMS): m/z
The above mechanistic hypothesis can also account for the
fact that at least two equivalents of TsNCl2 are needed for the
complete conversion. To further confirm the nucleophilic
mechanism of forming the 2-dichloromethyl group on the
imidazoline ring, the reaction (entry 1 of Table 1) was carried
out in carefully degassed acetonitrile in the absence of light.
‡
[M ‡1] found: 425.0500, calcd for C19H18O3N2SCl2: 425.0488.
4: 1H NMR (300 MHz, CDCl3): d ˆ 7.75 (d, J ˆ 8.5 Hz, 2H), 7.41 (d, J ˆ
8.5 Hz, 2H), 7.21 (s, 1H), 3.99 (s, 1H), 2.47 (s, 3H), 2.23 (s, 3H), 1.21 (s,
3H), 0.89 (s, 3H); 13C NMR (75 MHz, CDCl3): d ˆ 205.5, 153.5, 146.1,
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133.2, 130.4, 127.6, 70.4, 61.7, 30.7, 27.8, 23.2, 21.7; HR-MS (MALDI-FTMS):
diminished when a reduced amount of catalyst was used. Attempts to
further optimize the reaction conditions were also made by using a
variety of cosolvents of MeCN with other solvents, such as CHCl3,
CH2Cl2, toluene, and THF, in different ratios, but success was limited.
An excess amount of TsNCl2 (2.2 equiv) proved to be necessary for
the complete consumption of the olefin starting materials. With the
combination of rhodium/phosphane/4-Š MS in hand, we then went
back to examine the combination of triphenylphosphane with the
original rhodium compounds ([Rh(OAc)2]2 and [Rh(OOCCF3)2]2),
but failed to achieve any improvements. Surprisingly, when the
triphenylphosphane ligand was replaced by tributylphosphane, only a
tiny amount of the expected imidazolidine product was afforded, as
‡
m/z [M ‡1] found: 337.0484, calcd for C15H18O3N2SCl2: 337.0488.
5: 1H NMR (300 MHz, CDCl3): d ˆ 7.69 (d, J ˆ 8.4 Hz, 2H), 7.26 ± 7.18 (m,
6H), 6.88 (d, J ˆ 8.4 Hz, 2H), 5.21 (d, J ˆ 4.4 Hz, 1H), 4.56 (d, J ˆ 4.4 Hz,
1H), 3.81 (s, 3H), 2.42 (s, 3H); 13C NMR (75 MHz, CDCl3): d ˆ 169.7,
156.6, 145.7, 139.2, 133.8, 130.1, 128.8, 128.0, 127.7, 125.8, 72.0, 69.2, 61.4,
‡
53.1, 21.6; HR-MS (MALDI-FTMS): m/z [M ‡1] found: 441.0446, calcd
for C19H18O4N2SCl2: 441.0437.
6: 1H NMR (300 MHz, CDCl3): d ˆ 7.70 (d, J ˆ 8.4 Hz, 2H), 7.26 ± 7.19 (m,
6H), 6.90 (d, J ˆ 8.4 Hz, 2H), 5.20 (d, J ˆ 4.3 Hz, 1H), 4.55 (d, J ˆ 4.3 Hz,
1H), 4.23 (q, J ˆ 7.1 Hz, 2H), 2.42 (s, 3H), 1.29 (t, J ˆ 7.1 Hz, 3H); 13C NMR
(75 MHz, CDCl3): d ˆ 169.3, 156.6, 145.7, 139.3, 133.9, 130.0, 128.8, 128.0,
127.7, 125.8, 72.1, 69.3, 62.3, 61.5, 21.6, 14.0; HR-MS (MALDI-FTMS): m/z
1
revealed by crude H NMR analysis.
[13] L. I. Krimen, D. J. Cota, Org. React. 1969, 17, 213 ± 325.
[14] S.-J. Chang, Org. Process Res. Dev. 1999, 3, 232 ± 234.
‡
[M ‡1] found: 455.0587, calcd for C20H20O4N2SCl2: 455.0594.
7: 1H NMR (300 MHz, CDCl3): d ˆ 7.70 (dd, J ˆ 1.8, 6.6 Hz, 2H), 7.27 ± 7.24
(m, 2H), 7.18 (s, 1H), 6.90 (d, J ˆ 8.2 Hz, 2H), 6.77 (d, J ˆ 8.0 Hz, 2H), 5.17
(d, J ˆ 4.4 Hz, 1H), 4.54 (d, J ˆ 4.4 Hz, 1H), 3.79 (s, 3H), 2.43 (s, 3H), 2.30
(s, 3H); 13C NMR (75 MHz, CDCl3): d ˆ 169.8, 156.4, 145.7, 137.9, 136.3,
133.9, 130.0, 129.4, 127.7, 125.7, 71.9, 69.2, 61.4, 53.1, 21.6, 21.1; HR-MS
‡
(MALDI-FTMS): m/z [M ‡1] found: 455.0597, calcd for C20H20O4N2SCl2:
455.0594.
8: 1H NMR (300 MHz, CDCl3): d ˆ 7.83 (dd, J ˆ 1.9, 6.6 Hz, 2H), 7.38 (dd,
J ˆ 1.9, 6.6 Hz, 2H), 7.05 (s, 1H), 4.33 (s, 1H), 3.68 (s, 3H), 2.46 (s, 3H), 1.26
(s, 3H), 1.12 (s, 3H); 13C NMR (75 MHz, CDCl3): d ˆ 168. 5, 153.3, 145.6,
134.3, 130.0, 127.8, 70.9, 69.5, 61.4, 52.3, 29.3, 23.1, 21.7; HR-MS (MALDI-
Efficient, Catalytic, Aerobic Oxidation of
Alcohols with Octahedral Molecular Sieves**
Young-Chan Son, Vinit D. Makwana, Amy R. Howell,
and Steven L. Suib*
‡
FTMS): m/z [M ‡1] found: 393.0437, calcd for C15H18O4N2SCl2: 393.0449.
Received: June 18, 2001 [Z17296]
The oxidation of alcohols to carbonyl compounds is of great
interest to the fine chemicals industry and academia. Re-
cently, catalytic oxidations of alcohols in which oxygen is the
secondary oxidant have been the focus in many laborato-
ries.[1±6] Alcohol oxidations using Ru,[2] Co,[3] Cu,[4] Pd,[5] and
Pt[6] metal catalysts with additives, such as potassium carbo-
nate, sodium bicarbonate, pyridine, molecular sieves, and
phenanthroline, have been reported.
Stoichiometric metal oxidants such as chromates and active
manganese dioxide have also been widely used.[7] In fact,
conventional active manganese oxide has been most com-
monly used for allylic and benzylic oxidations. The reactivity
of active manganese oxide is dependent on preparation
methods, compositions, and structure.[7b, 8] Complicated prep-
aration methods are often necessary, and the use of freshly
made active manganese oxide is required. Moreover, five to
fifty equivalents of this reagent are required to obtain
oxidation products, which results in large amounts of non-
reusable, toxic waste.
[1] a) E. Block, A. L. Schwan in Comprehensive Organic Synthesis, Vol. 4
(Eds.: B. M. Trost, I. Fleming, M. F. Semmelhack), Pergamon, Oxford,
1991, pp. 329 ± 362; b) L. S. Hegedus in Comprehensive Organic
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[2] a) B. M. Trost, A. B. Pinkerton, J. Am. Chem. Soc. 2000, 122, 8081 ±
8082; b) B. M. Trost, A. B. Pinkerton, Angew. Chem. 2000, 112, 368 ±
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[3] For leading reviews of multicomponent reaction, see a) A. Dömling, I.
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[7] G. Li, H.-X. Wei, S. H. Kim, Tetrahedron Lett. 2000, 41, 8699 ± 8701.
[8] M. R. Grimmett in Comprehensive Heterocyclic Chemistry, Vol. 5
(Eds.: A. R. Katritzky, C. W. Rees), Pergamon, Oxford, 1984,
pp. 345 ± 457.
The problems associated with active manganese oxides
prompted us to examine octahedral molecular sieves (OMS)
as potential catalysts for alcohol oxidations. OMS materials
[9] D. Lucet, T. Le Gall, C. Mioskowski, Angew. Chem. 1998, 110, 2724 ±
2772; Angew. Chem. Int. Ed. 1998, 37, 2580 ± 2627.
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Aldrichimica Acta. 1996, 29, 3 ± 11; c) H. M. L. Davies, Aldrichimica
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[12] The common quenching treatment with aqueous Na2SO3 for N,N-
dichlorosulfonamide-based reactions was not used to avoid some
unknown side products. The loading of triphenylphosphane and the
rhodium(ii) heptafluorobutyrate dimer at 4.0 and 2.0 mol%, respec-
tively, turned out to be near the turnover point since the reaction was
not further accelerated in the presence of larger amounts of the
catalyst. On the other hand, both the reaction rate and yield were
[*] Prof. S. L. Suib
U-3060, Department of Chemistry
Department of Chemical Engineering and Institute of Materials
Science
University of Connecticut, Storrs, CT 06269 (USA)
Fax : (‡1)860-486-2981
E-mail: suib@uconnvm.uconn.edu
Y.-C. Son, V. D. Makwana, Prof. A. R. Howell
U-3060, Department of Chemistry, University of Connecticut
Storrs, CT 06269-3060 (USA)
[**] We acknowledge support of the Geosciences and Biosciences
Division, Office of Basic Energy Sciences, Office of Science, U.S.
Department of Energy. We also thank Professor Mark E. Davis, Dr.
Francis Galasso, and Dr. Lixin Cao for helpful discussions.
4280
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
1433-7851/01/4022-4280 $ 17.50+.50/0
Angew. Chem. Int. Ed. 2001, 40, No. 22