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Cyclopropanes by Nucleophilic Attack of Mono-and Diaryl-Substituted (3-Allyl)palladium Complexes Aryl Effect and Stereochemistry.

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the desired product 6 a (Table 1). [4-'3C]Nicotinic acid (99%
I3C) was prepared by using the method of Oberfrank et aI.l9]
and biosynthetically incorporated into ~rocanase.[~I
The cultivation of Pseudomorias putida nic I1 (a nicotinate auxotrophic
mutant), the isolation of the labeled enzyme. and the enzymatic
formation of the NAD+-imidazole propionate adduct were carried out as described by Klepp et aI.l4]250 mg (2.03 pmol) '%labeled urocanase and 48 mg (300 pmol) [5'-'3C]imidazole propionic acid . HCI were used.
Table 1. Spectroscopic data of compounds 5 a and 6a. N M R spectra in D,O, sodias reference for H, external dioxane as referum 3-trimethyl~ilyl-[~H,Ipropionate
ence (6 = 68.0) for " C N M R spectra. The water signal in the ' H N M R spectra was
suppressed by pre-saturation. A. 1. and P refer to the corresponding positions in
adenine. imidazole. and pyridiniiim rings. z and /$for the positions in the propionic
acid side chain.
l
~
8.8
5 a . 'H N M R (600 MHz; D,O. p D = 9.0): 6 = 8.88 (d. 'J(H2."C4)
=
l
8.6
~
8.4
8.2
,
~
8.0
7.8
l
7.6
~
I
7.4
- 6
5.4 Hz. 1 H,
P2).X.78(t,'J(H6."C4J=6.2Hz,3J(H6,HS)=6.8H~,1H,P6).8.33(s,1H,A8),
Fig. 2. Low-field portion of the ' H NMR spectrum of the [4-'3C]NAD+-[5'-''C]
8.01 (s. 1 H. A2). 7.93 (dd. 'J(HS,I3C5') = 6.7 Hz, 'J(HS.H6) = 6.8 Hz, 1 H. P5),
imidazole propionate adduct 5a.
7.61 (d, 'J(H2',I3C5' = 9.5 Hz, 1 H. 12'); ' H N M R (400 MHz; D,O, p D = 9.0):
6 = 3.05 (dt. 'J(/$-H. 1-H) =7.0 Hz, 'J('H,''C) z 2 Hz. 2 H , B-H). 2.47 (t. 3J(z-H.
/I-H) =7.0 Hz. 2H. z-H); ' T N M R (100 MHz; D,O. p D = 8.0. ca. 320 pg):
6 =130.12 (d, ' J ("CS""C'4)
- 7 0 H z , 1C. CS'). 151.12 (d. 'J("C4.
group of the side chain of the imidazole propionic acid portion
"CS') =70 HL. l C , C4).
of the adduct 5 a (not shown).
6a: 'H NMR (400 MHz; D 2 0 . p D = 4.6): ri = 2.60 (t, 'J(z-H, p-H) =7.3 Hz, 2 H ,
All these findings support structure 5 proposed by Klepp
z-H). 2.96 (dtr, 'J(/I-H. z-H) =7.3 Hz. 'J('H,"CJ = 4.4 Hr. 2 H . B-H), 7.20 (dd,
'J('H,''CC) = 2 0 0 . 3 H ~ . ~ J = 1 . 3 H
~ ~H. , H S ' ) . ~ . ~ ~ ( ~ ~ , ' J = S . ~ H Z . ~ Jet= al.
~ . [41
~ Hfor
Z .the isolated NAD +-imidazole propionate adduct. In
1 H. H2'); I 3 C N M R (100 MHz: D,O, p D = 3.9): 6 = 20.99 (B-C). 34.80 (z-CJ.
this light the mechanism of the urocanase reaction outlined in
116 44 (CS'). 133.85 ( C 2 ) .133.69 (C4'). 179 25 (COOH); MS (70 eV) im11;: 141.14
Scheme 3 seems to be even more likely.
[ M 'I.
Received: February 3, 1994 [Z 6665183
German version: Angew. Chem. 1994, 106, 1331
In the 13CNMR spectrum (Table 1) of the partially purified
doubly labeled adduct 5 a (Fig. 1) two doublets at 6 = 130.1 and
155.1 with a coupling constant of 70 Hz are discernible, which
154
152
150
148
146
144
142
-
140
138
136
134
132
130
128
6
Fig. 1 . Low-field portion of the "CNMR spectrum of the [4-'3C]NADt-[5'-13C]
imidazole propionate adduct 5a.
is consistent with a direct 13C-13Ccoupling. The singlet at
6 = 144.0 arises from unreacted [4-l3C]NAD+.In the low-field
portion of the 'H NMR spectrum of 5 a (Fig. 2; Table 1) most of
the signals are identical with those of the adduct 5 formed from
~ ] detects
[4-' 'CC]NAD' and [2-13C]imidazole p r o p i ~ n a t e . [One
an additional coupling of 3 3 = 6.7 Hz in the 5-H signal
(6 =7.93) of the nicotinamide ring (vicinal coupling with the
5'-I3C atom of the imidazole nucleus), and the 2'-H signal (doublet; 6 =7.61) of the imidazole shows also a vicinal coupling
constant of 3 J = 9.5 Hz, instead of the direct one of
' J = 212 Hz in the spectrum of 5.14]An additional vicinal 'HI3C coupling is discernible also in the signal of the 8-methylene
1280
c VCH Vrrlag~ge~ellriliafr
mbH D-69451 Wmlieim 1994
[l] L. H. Matherly. C. W. DeBrosse. A. T. Phillips, B/ochen?isrrj 1982, 21. 27892794.
[2] L. H. Matherly. K. A. Johnson, A. T. Phillips, Biochemistry 1982, 21, 27952798.
[3] R. M. Egan. L. H. Matherly, A. T. Phillips. Biochemislrj 1981. 20. 132-137.
[4] J. Klepp. A. Fallert-Muller. K. Grimm, W. E. Hull, J. Retey, Eur. J Biochewi.
1990. 192. 669-676.
[5] A. Pfaltz, S. Anwar. 72trahedron Lett. 1984, 25. 2977-2980.
[6] H. J. Barber, J. Chem. Soc. 1943, 79.
[7] R. W. Wynn. A. H. Corwin, J. Org. Chem. 1950, 15, 203-208.
[XI T. Furuta. M . Katdyama, H. Shibasaki, Y. Kasuya, J. Chem. Soc. Prrkrn Trans.
11992,1643-1648.
[9] M. Oberfrank. W. E. Hull, J. Retey, Eur. J. Biuchrm. 1984, 140, 157-161.
Cyclopropanes by Nucleophilic Attack of Monoand Diaryl-Substituted (q3-Ally1)palladium
Complexes : Aryl Effect and Stereochemistry **
Andreas R. Otte, Andreas Wilde, and
H. M. R. Hoffmann*
The reaction of (q3-allyl)palladium complexes with stabilized
carbon nucleophiles has matured into a major process for the
formation of carbon-carbon bonds."] More recently the (q31,3-diphenylallyl)palladium complex 1 has been investigated in
['I
Prof. Dr. H. M. R. Hoffmann, Dip].-Chem. A. R. Otte. Dr. A. Wilde
lnstitut fur Orgdnische Chemie der Universitat
Schneiderberg 1 B, D-30167 Hannover (FRG)
Telefax: Int. code + (511)762-3011
[**I This work was supported by Deutsche Forschungsgemeinschaft and by Fonds
der Chemischen lndustrie (PhD fellowship for A. W.). We thank Erhard Barho
for experimental contributions and Degussa AG for their generous gift of
palladium salts.
0570-0833/94 1212-1280 S 10 OOf 2510
Anpen Chem Int Ed Engl 1994, 33, N o 12
l
COMMUNICATIONS
great detail with respect to asymmetric allylic alkylation, and
experimental conditions have been established for high asymmetric induction by using a wide variety of bidentate ligands
(Pip. N!P. N/N, N/S).'']
We now show that a slight change of nucleophile and ligand
alters the product type decisively from that of allylic alkylation
to (substituted) cyclopropane, by attack of the nucleophile at
the central carbon of the ally1 ligand. Thus, complex 1 reacted in
the presence of the bidentate N/N ligand tmeda (N,N,N',N'tetramethylethylenediamine) with the lithium enolate of ester 2a
to give trisubstituted cyclopropane 3 a (Scheme 1). This cyclo-
allows the indirect introduction of an unsubstituted acetic acid
moiety after desilylation (3g -+ 3h).
The monophenylated (q3-1 -phenylallyl)palladium complex 4
gave disubstituted cyclopropanes in good yields (Scheme 2,
Table 2). However, attempts to transform simple alkyl-substitut-
bpd:J
Ph
O
H
+
.TMEDq
THF, CO
-15
Me0
OC
4
2a
5a (70%)
Scheme 2. Analogous reactions see Table 2.
MeU
-15
Ph
2a
O C
Table 2. 1runs-l,2-Disubstituted cyclopropanes from the (q3-l-phenylallyl)palIadium complex 4.
1 '\
1
Me0
Nucleophile [a] No.
3a (48%)
Scheme 1 LDA
=
Lithium diisopropylamide: analogous reactions see Table 1.
2b
Table 1. ii.r-Diphenyl-substituted cyclopropanes 3 from the (q3-1,3-diphenylally1)palladium complex 1.
Nucleophile [a] No.
R (n)
Product [b]
No.
Yield [%I [c]
3h
53 [e]
2c
R
No.
Product [b]
NMe,
CHMe,
p-MeO-C,H,
Yield [%] [c]
67 Id1
57 (el
R
oiNkb
56 [d]
23 [dl
5c
H
CHMe,
Ph
q,
R
2b:
R
0
0
NMe,
CHMe,
p-Me,N-C,H,
48 I 4
35 [el
Ph
2c
02Y
U
20
O+
p-MeO-C,H,
CcMs
0
[a] Bases for deprotonation: see Table 1. [b] All products were fully characterized
by spectroscopic methods. [c] Isolated yields. [d] Reaction temperature: - 15 "C.
[el Reaction temperature: -60°C. [fl Mixture of diastereomers (not Separable by
column chromatography).
Ph
b.Ph
3e
35 [dl
25 Id1
Ph
31
34 [dl
48 Id]
R%
Me02C
h,h
ph
iCH*)n
[a] Bases for deprotonation of the protonated nucleophile: lithium diisopropylamide (LDAj/TMEDA for esters, acid amides. and sulfones; potassium
bis(trimethylsilyljamide (KHMDS) for ketones, oxazolidinone derivatives, and
methyl trimethylsilylacetate. [b] All products were fully characterized by spectroscopic methods (IR, ' H and 13CNMR spectroscopy, mass spectrometry, and highresolution mass spectrometry). [c] Isolated yields. [d] Reaction temperature:
-15'C. [el Reaction temperature: -35 "C. [f] F- quant.
ed (q3-ally1)palladium complexes into cyclopropanes were not
promising. For example, the (q3-butenyl)palladium complex reacted with a-branched ester enolates, but not with other nucleophiles. Furthermore, introduction of a second methyl group as
in the ($-I ,3-dimethylallyl)palladium complex 6 provided no
cyclopropanes at all, even when using experimental conditions
optimum for converting the parent (q3-allyl)palladium complex
into cycI~propanes.[~I
In contrast, introduction of a single phenyl group as in the
(~3-l-methyl-3-phenylallyl)palladium
complex 7, afforded cyclopropanation products in good yields (Scheme 3 ) . Apparently,
the phenyl substituent facilitates cyclopropanation (aryl effect)
for reasons which are not completely clear at present.
i-p<J
'
propanation reaction is not limited to deprotonated esters, also
deprotonated acid amides, modified Evans enolates (cf. 2c),
ketones. and sulfones afforded corresponding three-membered
rings. Bulky tertiary carbanions were especially useful and reacted more satisfactorily than secondary carbanions (Table 1).
The silylated nucleophile from methyl trimethylsilylacetate 2g
Airg~a..C'lii~iii. 1111. Ed. E q l . 1994, 33, N o . 12
c yclopropanation
+ N u-
conditions
2a
LDA, TMEDA
THF, CO, -W0C
no cyclopropane
formation
6
)-Pd/T
' +2
b
Ph
Me0
8 (82%)
Ph I
Scheme 3.
7'.' ~VCH
_ ~ ~ r l u ~ s ~ i , s e l l s t .mbH,
l r u ~ f0.69451
f
WeinAeim. 1994
0S70-0833/94jl212-1281 S 10.00+ .25/0
1281
COMMUNICATIONS
The cyclopropanation was also applied to p-lactams, which are
of potential interest in medicinal chemistry. Again, preparation
of the mixed 1-methyl-2-phenylcyclopropane derivative with
complex 7 was feasible (Scheme4). Regarding the stereochemisPh
LDA,TMEDA 0
THF,CO
*
- 3 5 ~
I
Ph
+
pi
Ph
.
Ph
__
9 65%
0
LDA,TMEDA
THF, CO
+
Ph
-6OOC
10 24% (6: l)tal
1
11 38% ( 6 : l)Ia]
Scheme 4. [a] Mixture of diastereomers (not separable by column chromatography).
try, the phenyl groups, which are W-configurated in the q3-allyl
complex 1, are cis to each other in the products and therefore,
potentially repel each other. The incoming nucleophile is trans
to the two phenyl groups. Similarly, the W-configurated q3-allyl
complex 7 furnishes cyclopropane derivatives 8 (Scheme 3) and
11 (Scheme 4), in which the methyl and phenyl groups are cis to
each other. Thus, in all reactions studied the formation of substituted cyclopropane is clearly disrotatory (1 3 examples) .r41
In summary, nucleophilic cyclopropanation of (q3-allyl)palladium complexes is facilitated by terminal phenyl groups relative to methyl groups in the allyl ligand (aryl effect). The cyclopropanes are built up stereoselectively, and a quarternary carbon center['] exocyclic to the three-membered ring is installed
with ease.
Esperirnentul Procedure
Tetrahydrofuran was distilled over sodium:benzophenone under nitrogen. (?$Allyl)palladium complexes were prepared from allyl alcohols or ally1 chlorides by the
method of Bosnich et al. [2a].
General procedure for generating carbanions: To a solution of lithium diisopropylamide (LDA) (1.1 mmol) o r potassium bis(trimethylsily1)amide (KHMDS)
(1.66mL. 1 1 mmol. 15 'A in toluene) in dry T H F ( 5 mL) under nitrogen was added
the protonated nucleophile (1.1 mmol) at -78 'C. After the solution had been
stirred for 10 min it was warmed up to 0 'C and 10 min later recooled to -78 'C.
If LDA was used as a base, TMEDA (0.17mL, 1.1 mmol) was added. and the
resulting solution was stirred until required.
Cyclopropanation: The diiiieric (q2-allyl)palladiumchloride complex (0.275 mmol)
in dry T H F (5 mL) was placed in an oven-dried flask under nitrogen. The solution
was cooled to -78 C and TMEDA (0.17mL) was added. After warming the
mixture to the temperature given in the Tables. the carbanion solution (see above)
was added dropwise through a double-tipped needle. Attachment of B C O balloon
caused the reaction mixture to turn black and palladium to precipitate. After stirring for 30 min and warming to room temperature. the solvent was evaporated in
vacua and diethyl ether ( 5 0 mL) was added. The mixture was filtered and the filtrate
washed with water. The aqueous layer was re-extracted with diethyl ether and the
combined organic layers were washed with brine (20 mL). dried with MgSO,. and
concentrated. The resulting oil was purified by flash chromatography (silica gel,
cyclohexane!diethyl ether. 5 : 1) to give the product as a colorless oil or solid.
Spectroscopic data of 3a: ' H N M R (CDCI,. 200 MHz): 6 =7.02 (m. 10H. H,$,,,).
3.72(s.3H,OCH,).2.45(d.J=6Hz.2H.PhCH).2.09(t.J=6Hz.lH.cyclopropyl CH), 1.29 (s. 6 H , (CH,),C): " C NMR (CDCI,, 50 MHz. APT(Attached
Proton Test) technique: primary and tertiary carbons give negative (1) signals,
1282
,cj
VCH ~,/i.i.lu~.sgeJi,f/.sr.hofr
m b H . 0.69451 Wcrwhrnn, 1994
secondary and quarternary carbons give positive (t)signals: 6 = 177.78T. 137,841'.
128.961, 127.731, 125.731, 51.911, 41.71T. 33.491, 27.411, 23.481.
Received: January 20, 1994 [Z 6635 IE]
German version: Angeii. Chem. 1994, f06,1352
[l] B. M. Trost. Angrw. Chem. 1989, 101, 1199: A n g e n . Chetn. Inr. Ed. Engl. 1989.
28. 1173: B. M. Trost, T. R. Verhoeven in Coniprehensiw Orgunomerulhc Cherirrtry, Vol. X (Eds.: G. Wilkinson. F. G. A. Stone, E. W. Abel). Pergamon, Oxford, 1982, p. 799: S. A. Godleski in Cnniprehen.~iveOrgunic Sjnihesb, W .4
(Ed.: B. M. Trost), Pergamon. Oxford, 1991. p. 585: J. TSUJI.Tetrahedron 1986,
42. 4361.
[2] a) (PIP): P. B. Mackenzie. J. Whelm. B. Bosnich. J A m . Chein. Sor. 1985. 107.
2046; M . Sawamura, H. Nagata. H. Sakamoto. Y. Ito, ihid. 1992, 114. 2586:
B. M. Trost. Orgunornarullic's 1985,4, 1143: T. Hayashi, A . Yamamoto, T. Hagihara. Y. Ito, TrrruAerlron Lett. 1986, 27. 191 : Y. Okada, T. Minami, Y. Sasaki. Y.
Umezu. M. Yamaguchi, ihirl. 1990. 3f. 3905 (monodentate P Iigands): M. Yamaguchi, T. Shima, T. Yamagishi, M. Hida, ihirl. 1990, 31, 5049: Y. Okada, T.
Minami. Y Umezu, S. Nishikawa, R. Mori. Y Ndkayama. Tefruhedron A.s,vmn i e r r j 1991, 2. 667: C Breutel. H. Landert, A. Schnyder. F. Spindler. A Tijani,
A. Togni, J A m Chent S or... 1994. 116,4062: C. Breutel, A. Schnyder, A. Togni.
Chirniu 1993. 47, 283; b) (NIP), (N/N): P. von Matt, A. Pfaltz, Angew. <.'hem.
1993, 105. 614: Angrw. CAem. I n / . Ed. Engl. 1993, 32. 566; J. Sprinr. M. Kiefer.
G. Helmchen. M. Reggelin, G. Huttner, 0.Walter, L. Zsolnai. Tetruhedron Leri.
1994, 35. 1523: c)(N,"): A. Togni, TL.trahedron: A,ynirnPtuJ, 1991. 2. 683; V.
Leutenegger, G. Umbricht, C. Fahrni, P. von Matt, A. Pfaltz, fidlruhedron 1992,
48,2143: H.Kubota, M. Nakajima, K. Koga. Tetruhedron L ~ I I1993.34,
.
8135:
d)(N/S): C. G. Frost. J. M. J. Williams. ;hid. 1993. 34. 1785: G . J. Dawson.
C. G. Frost, C. J. Martin. J. M. J. Williams. S. J. Coote. rhid. 1993, 34. 7793:
e) Reviews: C. G. Frost, J. Howarth, J. M. J. Williams. Tetruhrdron: AJymrnefry
1992. 3. 1089: 0. Reiser, Angew. Chem. 1993. 105. 576;Angew. Cliem. 1iu. Ed.
Engl. 1993, 32. 547: A . Pfaltz. Acc. Chern Res. 1993. 26, 339.
[ 3 ] H. M. R. Hoffmann. A. R. Otte. A. Wilde. Angel$. Chefn. 1992, 104, 224;
Angew. Chern. Inr. Ed. Engl. 1992, 31. 234; A. Wilde. A. R. Otte. H. M. R.
Hoffmann. J. Chem. Suc. Chcrn. Cornmun. 1993,615; C. Carfagna. R. Galarini,
K. Linn, J. A. Lopez, C. Mealli. A. Musco. Organomerallics 1993. 12. 3019: C.
Carfagna, L. Mariani, A. Musco. G. Sallese. R. Santi, J Org. Chem. 1991. 56.
3924: L . S. Hegedus. W. H. Darlington. C. E. Russel, ibid. 1980, 45, 5193.
[4] The stereochemistry bas elucidated by differential NOE spectroscopy.
[5] Reviews: S. F. Martin. Tetruherlron 1980. 36,419: K. Fuji. Chem. Rev. 1993. Y3,
2037.
Copper(I1)-Mediated Oxidative Coupling of
Bis(dimethylaminomethy1)arylruthenium
Complexes to give [ (terpy)Ru"'(pincer-pincer)Rd1'(terpy)J(CuC1,),J;"
Jean-Pascal Sutter, David M. Grove, Marc Beley,
Jean-Paul Collin, Nora Veldman, Anthony L. Spek,
Jean-Pierre Sauvage, and Gerard van Koten*
In the course of our studies on the catalytic, electro-, and
photochemical properties of bis(dimethylaminomethy1)aryl
metal complexes in which the aryl ligand is the monoanionic
[*I
['I
[**I
Prof. Dr. G. van Koten, Dr. J:P. Sutter. Dr. D. M. Grove
Debye Institute, Department of Metal-Mediated Synthesis. Utrecht University
Padualaan 8. NL-3584 CH Utrecht (The Netherlands)
Telefax: Int. code i(30)523615
Dr. M. Beley, Dr. J.-P. Collin, Dr. J.-P. Sauvage
Labordtoire de Chimie Organo-Minerale, Universite Louis Pasteur (France)
N. Veldman. Dr. A . L. Spek[+'
Bijvoet Center for Biomolecular Research.
Laboratory of Crystal and Structural Chemistry, Utrecht University
Padualaan 8. NL-3584 C H Utrecht, Utrecht (The Netherlands)
Address queries related to the crystallographic study to this author.
This work was supported in part (A L. S. and N. V.) by the Netherlands
Foundation of Chemical Research (SON) with financial aid from the Netherlands Organization for Scientific Research (NWO). This collaborative work is
part of a COST-D4 approved programme. Ligand abbreviations: pincer =
[2,6-(Me,NCH,),C,H,I-.
pincer-pincer = [2,6-(Me,NCH2),C,H, - C,H,-2.6(CH,NMe,),]'-.
dpb-dpb = [2,6-(2-pyridyl),C,HZ -C,H,-2,6-(2-pyridyl),12 -,
tterpy = 4'-(p-tolyl)-2.2': 6,2"-terpyridine. terpy = 2.2': 6',2"-terpyridine.
+
0570-0~33;94:1212-12X2S 10.00 .25i0
Angebi.. Chem. Inr. Ed. Engl. 1994, 33, No. 12
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