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Diastereo- and Enantioselective Michael Addition Initiated Cyclizations to trans-Substituted Cyclopentanecarboxylates.

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a good hydrogen bonding function in the vicinity of the
stereogenic center.
Received: June 13. 1991 [Z 4704 IE]
German version: Angew. Chem. 103 (1991) 1685
Publication delayed at authors' request
[I] G. Hesse, R. Hagel, Chromutogruphiu 6 (1973) 277-280.
[2] A. Mannschreck, H. Koller. R. Wernicke, Kontukte (Durmstudt) 1985,
40-48.
[3] E. Francotte, R. M. Wolf, Chirulitj, 3 (1991) 43-55.
[4] Review: Y. Okamoto, R. Aburatani. Poljm. N e w 14 (1989) 295-301.
[5] Review: W. H. Pirkle, T. C. Pochapsky, Chum. Rev. 89 (1989) 347-362.
[6] Review: G. Blaschke, Chromufogr. Sci. 40 (1988) 179-198.
[7] a) G. Blaschke, A. Schwanghart, Chem. Ber. 109 (1976) 1967-1975: b)
Sold as an analytical HPLC phase under the name Chiraspher" by E.
Merck. Darmstadt.
[XI U. Schwartz, R. Grosser. K. E. Piejko. B. Bomer. D. Ark. EP-B 218089
(1987). Bayer AG.
191 G. Blaschke, W. Broker, W. Fraenkel, Angew. Chem. 98 (1986) 808-810;
Angew. Chem. Int. Ed. Engl. 25 (1986) 830-831
1101 B. Bomer. R. Grosser. U. Schwartz. D. A r k K. E. Pieiko. EP-B 282770
(1988). Bayer AG.
a) D. Seebach, S. G. Muller. U. Gysel, J. Zimmermann, Helv. Chim Actu
71 (1988) 1303-1318; h)U. Gerlach, T. Haubenreich,S. Hunig. N. Klaunzer, Liebigs Arm. Chem. 1989.103- 104; c) A. Hallberg, R. Isaksson, A. R.
Martin, J. Sandstrom, J. Am. Chem. Soc. l / / (1989) 4387-4392.
0. Wallach, Justus Liebigs Ann. Chem. 276 (1893) 296-327.
Examples ofpreparation: W. Lange. B. Bomer, R. Grosser, D. Arlt, EP-A
379917 (1990), Bayer AG.
Suitab1earee.g. LiChrosorbX-DIOL5 p n from E. Merck, Darmstadt and
Nucleosil*-OH 5 pm from Macherey and Nagel. Duren. For instructions
see e.g. refs [9] and [ 131.
H. Engelhardt, H. Low, W. Eberhardt, M. Mauss, Chromutogruphiu 27
(1989) 535-543.
We would like to thank Prof. Dr. H. Engelhurdt, Dr. H. Low, and Dipl.
Chem. W Gotringer of the University of Saarbriicken for discussions and
providing vinylsilica.
Preparation of vinylsilica: 10 g silica gel (Si 100, 5 pm) dried at 120 "C
under high vacuum was suspended in 100 mL toluene, treated with 7 g
trichlorovinylsilane, and heated at reflux. After the addition of 12.4 g
triethylamine in 30 mL toluene the mixture was stirred for 16 h at 110 -C.
The vinylsilica was washed with toluene. methanol, and dichloromethdne
and dried under high vacuum at 70 "C. Yield: 10.6 g; C,H analysis: 3 % C,
0.8% H. Preparation of CSPs: 3 g monomer, 3 g vinylsilica, and 60 mg
AIBN were stirred with 15 mL chloroform under nitrogen for 2 ha t 65 "C.
The product was filtered off under suction, washed with chloroform,
dimethylformamide, and 2-propanol, and dried under high vacuum at
25 "C. Yield: 3.1-3.2g; polymer coating 10-15%.
oxymethylpyrrolidine) are proven chiral Michael donors,[41
asymmetric MIRC reactions (Michael-Znitiated Ring Closure)[51of the type C -+D should be possible with high
stereoselectivity. The 1,2-disubstituted cycloalkanes D with
various nucleophile (Nu) and acceptor (Acc) functional
groups in both side chains are important building blocks in
the syntheses of bioactive compounds and natural products
containing five-membered rings.I6]
intramolecular
_1.4-addition
__--__--~
A
B
rx
intermolecular
_1.4-addition
_ _ _ _ _ _+
--Nu
D
C
We report here the synthesis of highly diastereo- and enantiopure trans-disubsti tuted cyclopentanecarboxylates 4 by
the MIRC reaction of SAMPiRAMP hydrazones 1 with
methyl (E)-6-bromo-hex-2-eriOate (2). SAMP hydrazones
(9-1
available
,
from the corresponding methyl ketones, are
metalated with lithium diisopropylamide at 0°C and then
treated with the w-functionalized Michael acceptor at
- 78 "C. After workup the cyclized (E/Z)-hydrazones are
n
Diastereo- and Enantioselective Michael Addition
Initiated Cyclizations to trans-Substituted
Cyclopentanecarboxylates **
By Dieter Enders,* Hermann J. Scherer, and Gerhard Raabe
Scheme 1. LDA = lithium diisopropylamide. a, R
R = iBu; d, R = Ph; e, R = p-BrC,H,.
Dedicated to Professor Kurt Schaflner
on the occasion of his 60th birthday
Intramolecular Michael additions are frequently used in
the construction of cyclic systems (A + B).['] If the primary
addition product of an intermolecular Michael addition is
intercepted with a tandem intramolecular reaction, cyclic
products may be obtained too (C -+ D).[2,31
Because metalated SAMPiRAMP hydrazones (SAMP = (9-1-amino-2methoxymethylpyrrolidine, RAMP = (R)-1 -amino-2-meth[*] Prof. Dr. D. Enders, Dipl.-Chem. H. J. Scherer, Dr. G. Raabe
Institut fur Organische Chemie der Technischen Hochschule
Professor-Pirlet-Strasse 1. W-5100 Aachen (FRG)
[**I This work was supported by the Fonds der Chemischen Industrie. We
thank Degussa AG, BASF AG, Bayer AG, and Hoechst AG for providing
us with chemicals.
1664
8 VCH ~r1ugsgesellsrhuJfmbH. W-6940 Weinheim. 1991
=
Me; b, R = nBu; c.
obtained, which may be purified by chromatography and
characterized. Usually the crude products 3 are converted
directly to the final products (1 S,2R)-4 by oxidative cleavage
with ozone. After chromatographic purification the transdisubstituted cyclopentanecarboxylates 4 are obtained in
43-78% total yield and with high diastereomeric (de 2 9599 %) and enantiomeric excesses (ee 2 95-97 %) (Table 1).
The de values for the cyclization products 3 and 4 were
determined by 13C NMR spectroscopy; the ee values for
compounds 4a-c, by gas chromatography with a chiral permethylated P-cyclodextrin stationary phase. The determination of the enantiomeric excesses of 4d, e was possible by
means of 'H NMR experiments using the shift reagent
0~70-0~~33J9111212-/664B
3.50+.25/0
Angew. Chem. In!. Ed. Engl. 30 (1991) No. I2
Table 1 . trans-Disubstituted cyclopentanecarboxylates4 obtained by asymmetric MIRC reaction.
4
R
yield
[a]!T
[%I [a1 (c, CHCI,)
de [%] [h]
ee [ %] [b]
(lS,2R)-4a
(lS,2R)-4b
(lS,2R)-4c
(1R,2S)-4c [d]
(1S,2R)-4d
(IS,2R)-4e [f]
Me
nBu
iBu
iBu
Ph
p-BrC,H,
54
43
78
62
77
73
299
>95 [c]
>97
>97
> 9 6 [c]
>96 [c]
t 97
295
> 96
> 96
> 9 6 [el
>95 [el
+51.1 (2.20)
+39.7 (1.87)
+47.4 (1.03)
-47.6 (2.02)
f63.8 (1.76)
+48.3 (1.12)
[a] The yields are for the MIRC reaction and subsequent ozonolysis without
isolation of the hydrazone intermediates 3. [b] Determined by gas chromatogra115"C, 1 bar H,,
phy on a chiral stationary phase (permethyl-B-cyclodextrin,
see Fig. 1). [c] Determined by I3C NMR spectroscopy. [d] RAMP was used as
chiral auxiliary. [el Determined by 'H NMR Lanthanide Induced Shift (LIS)
with [Eu(hfc),]. [f] M.p. = 46-47°C.
[Eu(hfc),], . The racemic trans-cyclopentanecarboxylates,
rac-4 a - e , required for comparison were prepared in high
diastereomeric purity from the corresponding dimethylhydrazone homocuprates according to the method previously
The MIRC variation described here offers a direct and
highly stereoselective approach to important synthetic building blocks.['4] Initial results show that this method can be
applied in the syntheses of rings of other sizes (three-, six-,
and seven-membered rings) as well as with other acceptors,
for example suIfones.["J
Experimental Procedure
To a stirred solution of 5.5 mmol lithium diisopropylamide [prepared from
0.78 mL diisopropylamine and 3.67 mL n-butyllithium solution (1.5 N in nhexane)] at 0°C under argon was added dropwise 5mmol hydrazone 1. The
mixture was stirred 2 h at 0°C and then cooled to -78°C before a solution of
5 mmol (a-2in 5 mL TH F was added dropwise. The reaction mixture was
stirred about 12 b during which time the temperature rose from -78°C to
0-10°C. After addition of 30 mL NH,CI solution and 50 mL ether, the phases
were separated. The aqueous phase was extracted with ether (2 x 50 mL). The
collected organic phases were washed with 10 mL saturated NaCl solution and
dried over Na,SO,/MgSO,. The solvent was removed under reduced pressure
and the crude hydrazone was dissolved in 30 mL CH,CI, and cooled to - 78 "C
under argon. Ozone was then passed through the solution at this temperature
until a blue-green color was observed. The excess ozone was dispelled by purging with an argon stream. Then the solvent was removed and the products were
purified by column chromatography (ether/petroleum ether 1 :3).
Received: July 30, 1993 124842 IE]
German version: Angew. Chem. 103 (1991) 1676
CAS Registry numbers:
1 a, 65651-52-7; 1 b, 137057-38-6; S-1 c, 137057-39-7; R-1 c, 137057-40-0; 1 d,
89393-53-3; l e , 137057-41-1 ; (E)-2, 75424-49-6; 4a, 135028-29-4; 4b, 137057,
(1 R, 2 S ) - 4 ~ 137170-92-4;
,
4d, 137057-36-4;
34-2; (1 S, 2 R ) - 4 ~ 137057-35-3;
4e, 137057-37-5.
0
(IS,2R)Qa
de: > 99%
rac4a
de: 98%
1
li
ee: 2 97%
1
Fig. 1. Determination of diastereomericand enantiomeric excesses by gas chromatography (fused silica capillary, heptakis(2,3,6-tri-O-methyl)-~-cyclodextrin
in OV 1701, 115"C, 1.0 bar H,) [7].
The relative and absolute configurations of the cyclopentanecarboxylates were unambiguously assigned by X-ray
structural analysis of compound 4e.I9- This product obtained from the SAMP auxiliary was determined to have an
(1S,2R) configuration. The simple change in auxiliaries from
SAMP to RAMP affords access to the other enantiomer
(Table 1). The absolute configuration (2R)of the stereogenic
center generated in the first step of the l,.l-addition is in
agreement with previous results of Michael additions with
SAMP hydrazones [41and the postulated mechanism of electrophilic substitutions with SAMP/RAMP hydrazones." 31
W
Fig. 2. X-ray crystal structure of (1S,2R)-4e [9]
Angew. Chem. Int. Ed. Engl. 30 (1991) No. 12
0 VCH
[I] a) D. A. Oare, C. H. Heathcock, Top. Stereochem. 19 (1989) 227; b) E.
Winterfeldt, Kontakte (Darmstadr) 1987, 37; c) G. Stork, N. A. Saccomano, Tetrahedron Lett. 28 (1987) 2087; d) G. Berthiaume, J.-F. Lavalee,
P. Deslongchamps, ibid. 27(1986) 5451 ;e) J.-F. Lavalee, G. Berthiaume, P.
Deslongchamps, F. Grein, ibid. 27 (1986) 5455; f) K. Shishido, Y.
Sukegawa, K. Fukumoto, T. Kametani, 1 Chem. SOC.
Perkin Trans. 1
1987, 993.
[2] M. J. Chapdelaine, M. Hulce, Org. React. ( N Y ) 38 (1990) 225.
[3] a) T. Hudlicky, J. D. Price, Chem. Rev.89(1989) 1467; b) M. P. Cooke, Jr.,
Tetrahedron Lett. 1979,2199; c) G. H. Posner, J. J. Sterling, C. E. Whitten,
C. M. Lentz, D. J. Brunelle, J. Am. Chem. Soc. 97 (1975) 107; d ) G . H
Posner, J. P. Mallamo, A. Y. Black, Tetrahedron 37 (1981) 3921 ; e) G. H.
Posner, Chem. Rev. 86 (1986) 831 ; f) R. D. Little, J. R. Dawson, 1 Am.
100 (1978) 4607; g) R. D. Little, R. Verhi, W. T. Monte, S.
Chem. SOC.
Nugent, J. R. Dawson, 1 Org. Chem. 47(1982) 362; h) W. A. Nugent, F. W.
. Hobbs, Jr.. ibid. 51
Hohhs, Jr., ibid. 48(1983) 5364; i) W A. Nugent, F. W
(1986) 3376; j) T. Uyehara, N. Shida, Y. Yamamoto, J. Chem. SOC.Chem.
Commun. f989,113; k) M. Yamaguchi, M. Tsukamoto, I. HirdO, Tetrahedron Lett. 26 (1985) 1723; I) Y. Inouye, S. Inamasu. M. Ohno. T.Sugita.
H. M. Walhorsky, J. Am. Chem. Soc. 83 (1961) 2962; m) H. Hagiwara, T.
Akama, A. Okano, H. Uda, Chem. Lett. 1989, 2149; n) S. Saito, Y Hirohara, 0.Narahara, T. Moriwake,J. Am. Chem. Soc. l l f (1989)4533; 0)C.
Fang, H. Suemune, K. Sakai, Tetrahedron Lett. 31 (1990) 4751; p) A. I.
Meyers, G. Licini, ibid. 30 (1989) 4049; q) M. Yamaguchi, K. Hasebe, S.
Tanaka, T. Minami, ibid. 27 (1986) 959; r) C . R. Nevill, Jr., P. L. Fuchs,
Synth. Commun. 20 (1990) 761.
[4] a) D. Enders, K. Papadopoulos, Tetrahedron Lett. 24 (1983) 4967; b) D.
Enders, K. Papadopoulos, B. E. M. Rendenhach, R. Appel, F. Knoch,
ibid. 27 (1986) 3491; c) D. Enders, B. E. M. Rendenhach, Tetrahedron 42
(1986) 2235; d) Chem. Ber. 120 (1987) 1223; e) D. Enders, B. E. M. Rendenbach in R. Greengalph. T. R. Roberts (Eds.): EnanfioselectiveSynthesis
of Bioregulators in Pesticide Science and Biotechnology, Blackwell, Oxford
1987, p. 17; f) D. Enders, A. S. Demir, B. E. M. Rendenbach, Chem. Ber.
120 (1987) 1731; g) D. Enders, A. S. Demir. H. Puff, S. Franken, Tetrahedron Lett. 28 (1987) 3795; h) D. Enders, S. Muller, A. S. Demir, ibid. 29
(1988) 6437.
[S] R. D. Little, J. R. Dawson, Tetrahedron Lett. 2f (1980) 2609.
[6] a) L. A. Paquette, Top. Curr. Chem. 119 (1984) 1; h) B. M. Trost, Chem.
SOC.Rev. 11 (1982) 141; c) B. M. Trost, Angew. Chem. 98 (1986) 1 ;Angew.
Chem. Inr. Ed. Engl. 25 (1986) 1; d) W. I. Taylor, A. R. Battersby (Eds.):
Cvclopentanoid Terpene Derivatives (Organic Substances of Natural
Origin. Vol. 2), Dekker, New York 1969.
[7] A. Kohnes, Dissertation, Technische Hochschule Aachen 1991.
[8] E. J. Corey, D. Enders, Chem. Ber. f f I (1978) 1337.
[9] Suitable crystals were obtained at -20°C from petroleum ether.
Orthorhombic, space group P2,2,2, (19) a = 6.005(2), b = 13.958(2),
c = 17.282(1) A, V = 1448.5 A3, M,,,, = 325.2, Z = 4, F(000) = 664,
pca,c= 1.491 g ~ m - ~
p =
, 30.11 cm-' (correction for spherical absorp-
Verlagsgesellschaft mbH, W-6940 Weinheim. 1991
0570-0833/91/1212-1665 $3.50+.25/0
1665
tion), Enraf-Noniius four-circle diffractometer, 0/2/1 scans, 20 "C. Mo,.
radiation (i
= 0.7169 A, graphite monochromator). 3336 independent reflections (fh + k +l), of which 2082 were observed [I>2u(1), R , =
0.0301, sinO/%,,, = 0.6 for solution and refinement. The structure was
determined by the heavy atom method using the XTAL2.6 program package. Positions of hydrogen atoms calculated, 173 parameters refined,
R = 0.053 (R, = 0.048), residual electron density 0.7 e k 3An
. enantiopole parameter'".'
refined to 0.004 confirms the absolute configuration
shown in Figure 2. Further details of the crystal structure may be obtained
from the Fachinformationszentrum Karlsruhe. Gesellschaft fur wissenschaftlich-technische Information mbH, W-7514 Eggenstein-Leopoldshafen 2, on quoting the depository number CSD-55614, the names of
the authors, and the journal citation.
[lo] S. R. Hall, J. M. Stewart (Eds.): XTAL2.6 User's Manual, Universities of
Western Australia and Maryland 1989.
[ l l ] H. D. Flack, Acta Cryslallogr. Sect. A39 (1983) 876.
[12] G . Bernardinelli, H. D. Flack, Acra Crystallogr. Secr. A4f (1985) 500.
1131 a) D. Enders in J. D. Morrison (Eds.): Asymmerric Synthesis Vol. 3, Academic, Orlando 1984, p. 275; b) D. Enders, Chem. Scrfpta 25 (1985) 139;
c) D. Enders, G. Bachstadter, K. A. M. Kremer, M. Marsch, K. Harms,
G. Boche, Angew. Chem. 100 (1988) 1580; Angew. Chem. I n l . Ed. Engl. 27
(1988) 1522.
[14] All new compounds gave correct elemental analyses and spectra (NMR,
IR, MS).
1151 D. Enders, H. Scherer, unpublished results; H . J. Scherer, Dissertarion,
Technische Hochschule Aachen 1991.
C6HSLi
C2H4
iBuNC
PMDTA
TMEDA
12
I1
butyl isocyanide, should likewise coordinate as masked acyl
carbanions to nickel(0) complexes.[718 reacts with [Ni(C,H,),]
in this sense in the presence of one equivalent of PMDTA
with formation of 11 (yellow crystals).1s1With TMEDA, 12
is obtained.
Nickel(o)-Carbene Complexes
By Barbara Gabor, Carl Kruger, Bernd Marczinke,
Richard Mynott, and Gunther WiEke*
Dedicated to Professor Horst Prinzbach
on the occasion of his 60th birthday
Isocyanides can be metalated, e.g. with n-butyllithium, in
the cr-position.['l We were interested whether [Ni(CNCH,),] 1
reacts with nBuLi in the same way to give [Ni(CNCH,Li),]
2. Compound 1, which is insoluble in pentane, dissolves when
treated in this solvent at -20 "C with four equivalents of
nBuLi. No liberation of n-butane is observed, either immediately or upon subsequent hydrolysis. Apparently, nBuLi
adds to the C=N bond, possibly with formation of [Ni{=C(C,H,)NLi(CH,)),] 3, which, however, could hitherto not be
isolated, since it undergoes secondary reactions.
Attempts to obtain 2 from LiCH,NC and [Ni(cod),] led to
displacement of 1,s-cyclooctadiene (cod) and loss of methylene to give Li,[Ni(CN),] 4,1z1which reacts with (CH,),SiCI
to the homoleptic complex of trimethylsilyl isocyanide
[Ni{CNSi(CH,),},] 5.[,] In a completely analogous way
[(tpp),NiCN][Li(thf),] 6 (tpp = triphenylphosphane) reacts
with (CH,),SiCl to give [(tpp),Ni{CNSi(CH,),}] 7.A compound analogous to 6 is formed from [Ni(cdt)] (cdt =
all-trans-I ,5,9-cyclododecatriene) and the addition products
8 of phenylltihium and tert-butyl isocyanide. Aside from
benzene and isobutene, formation of an adduct of LiCN and
[Ni(cdt)] is observed, in the presence of N,N,N'N-tetramethylethylenediamine (TMEDA) [ (cdt)NiCN][Li(tmeda),]
9 and of pentamethyldiethylenetriamine (PMDTA) [(cdt)NiCN][Li(pmdta)] 10. According to the NMR spectra all
three C=C bonds ofcdt are coordinated to the Ni atom. 9 and
10 can also be prepared directly from [Ni(cdt)] and LiCN.[41
[Ni(C,H,),] forms well-defined complexes with organolithium[51and organomagnesium compounds.[61Metalated
aldimines, such as the adduct 8 of phenyllithium and terr[*] Prof. Dr. G. Wilke, B. Gabor, Prof. Dr. C. Kriiger. Dr. B. Marczinke,
Dr. R. Mynott
Max-Planck-lnstitut fur Kohlenforschung
Kaiser-Wilhelm-Platz 1 , W-4330 Miilheim a. d. Ruhr (FRG)
1666
0 VCH
Verlagsgesellschaft mbH, W-6940 Weinheim, 1991
+ Hacac
+ CH,I
1
I
[2.1.1] Cryptand
- 30 OC. 68%
C,H,
I
14
13
I
-40°C,62%
O2
- CO - N,
X
I
X
C6H, - CO - N,
H
CH3
15
O2
16
Whereas lithiumacetyl- and lithiumcarbamoylnickel(o)
complexes cannot be converted into neutral nickel(0)-carbene
complexes,[g1the alkylation of 11 with CHJ in the presence
of [2.1 .l]cryptand successfully leads to formation of the neutral 16e nickel(o)-carbene complex 13.['01Without cryptand,
only amorphous products are obtained. The protonation of
11 with acetylacetone (Hacac) in ether leads in a comparable
way to 14.["] 13 and 14 precipitate in the form of orange-
0570-0833191j1212-1666$3.50+.25/0
Angew. Chem. Int. Ed. Engl. 30 (1991) N o . 12
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