close

Вход

Забыли?

вход по аккаунту

?

Cyclic Systems by Palladium-Catalyzed Oxidation of Diolefins.

код для вставкиСкачать
Received: August 2, 1979 [Z 326 IE]
German version: Angew. Chem. Y1. 930 (1979)
Under these conditions 5-methylenenorbornene (1) furnishes only the diFhlorinated nortricyclene derivative (2)'".
CAS Registry numbers:
( I ) , 63413-01-4; (31, 71888-45-4 (61, 71888-443; (71, 69178-16-1. (8). 71882-20-7:
(9).71901-53-6
111 Complexes with Carbon Sulfides and Selenides as Ligands, Part 2. This work
was supported by the Deutsche Forschungsgemeinschaft, the Fonds der
Chemischen lndustrie and by gifts of chemicals from BASF AG, Ludwigshafen, and DEGUSSA. Hanau. Germany. -Part I . 121.
[2] H. Werner, K. Leonhard, Ch. Burschka, J . Organomet. Chem. 160, 291
(1978).
(31 I S. Butler, N . J . Coudle, D. Cozak. J . Organomet. Chem. 133, 59 (1977): M.
Herberhold, M. Suss-Fink, Chem. Ber. 111. 2273 (1978).
14) 0.Kolb, Diplomarbeit, Universitrit Wurzburg 1979.
[ S ] K. Leonhard, unpublished results
[6] H. Werner. R. Feser. Angew. Chem. 91. 171 (1979); Angew. Chem. Int. Ed.
Engl. I X . 157 (1979).
[7] F. Faraone, G. Tresoldi, G. A . Loprete. J . Chem. Soc. Dalton Trans. 1979,
933.
[8] I . S. Buder. Acc. Chem. Res. 10. 359 (1977): B. D. Dombek, R. J. Angelici,
Inorg. Chem. 15. 1089 (1976); J. W. Buchler ef al.. Z . Naturforsch. B 33, 1371
(1978).
h
\\
PdCl,lCuClllHOAclNaOAc
25"C, 3 d , 75%
121
11)
CH,CI
This selective dichlorination is the result of a PdCl2/CuCl2
catalysis; CuCI, alone catalyzes only the addition of HCl or
HOAc to give (3), (4), and (5).
I
I31
lLl
/5/
CH3
P
I
t
48h
L
CH3
J
Reaction of the structurally related 5-vinylnorbornene (6)
(exo/endo = 24/76) with PdC12/CuClz/HOAc/NaOAc leads
to the isomeric brendane derivatives (7a) and (7b) in the ratio 7 :3; noncyclized chlorides are also formed.
Cyclic Systems by Palladium-Catalyzed Oxidation of
Diolefins'"]
By Andreas Heumann, Murius Reglier, and Bernard WaegelP'J
The direct catalytic oxidation of olefins (except ethylene['])
in the presence of palladium salts has only recently acquired
importance in synthetic organic chemistry[*].With the system
PdClz/CuC12/buffered acetic acid it is possible to add chlorine and the acetoxy group[41to strained olefins such as norbornenet3"' or ap~pinene['~I.
We have found that not only compounds from the norbornene series but also monocyclic and acyclic hydrocarbonsproviding they contain two double bonds-can be oxidized
selectively and in good yields with palladium salts. The reaction is of general utility [examples: (l),endo-(6), (lo), 5-methylenecyclooctene~5]]and proceeds according to the following Scheme:
Y 1x1
endo - 161
(7al
-,
The structures of the compounds (7)17]were confirmed by
degradation to the known 2-brendanone[']'; the position of
the chlorine can be assigned by mechanistic considerations.
-CI
lBal, X = C I
IBbl, X = OAc
L
I91
j
J
The base-catalyzed cleavage of HCl from (7) leads to 4brenden-2-01['1. The complexes (8a) and (Sb) can be isolatedll"1, and, at 80 "C, form the same products (7).
A formal a,w'-cyclization is observed on oxidation of cisand trans-1,2-divinylcyclohexane(1Oa) and (lob) to the bicyclo[4.3.0]non-6-enederivative (11).
On addition of CuCl, (2 mol per mol olefin) the reaction
becomes catalytic with regard to the palladium salt (PdC12
0.03 mol-%); the use of buffered (NaOAc) acetic acid as solvent facilitates the isolation of various types of disubstituted
final products. The second double bond in the substrate stabilizes the intermediary (and often isolable) Pd-a-complex
and, moreover, is inserted into the C-Pd bond. C -C coupling, i. e. cyclization, occurs and the a-ITcomplex affords a
new a-complex which can readily react by p-elimination 01
reductive elimination to give the metal-free final products.
['I
Prof. Dr. 8 . Waegell, Dr. A. Heumann, Dipl.-Chem. M. Reglier
Laboratoire de Stereochimie, associe au CNRS
Universite d'Aix-Marseille
Centre de St-JerAme, F-13013 Marseille (France)
[**I
This work was supported by the Delegation Gentrale a la Recherche Scien
tifique et Technique (DGRST: decision daide n" 77.7.0755).
866
0 Verlag Chemie, GmbH, 6940 Weinheim, 1979
The formation of the isomer (11) can be regarded as a sequence of several stereoselective steps proceeding via the intermediates (13) and (14)[". Apparently, the cis-isomer ( 1 0 ~ )
has the "correct" stereochemistry; according to model considerations, however, the frans-isomer (1Ob) should also yield
palladium complexes relatively easily. It can be seen that the
0570-0833/79/1111-0866
$ 02.50/0
Angen, Chem Inr. Ed. Engl. 1H (IY7Y) No. I /
chosen models lead not only to synthetically interesting reactions but also give an insight into the reaction mechanism[''.
PdC12 (3 mol-%), CuC12 [2 mol per mol (I)] and HOAc/
NaOAc affords the products (2) to (5) in the ratio
8 : 35 :20: 22 (Table 1)[*]. This reaction enables not only the
preparation of relatively complex systems from readily accessible olefins but also an insight into the mechanism of this
metal-catalyzed oxidative cyclization. The structures were
assigned on the basis of the following findings: On base-catalyzed HCI-elimination, hydrolysis, and subsequent hydrogenation the reaction mixture afforded bicyclo[3.3.l]nonan~ - O I [ ~and
] bicyclo[4.2.l]nonan-1-01[~~.
The endo configuration of the 4-chloro substituents in (2) and (3) can be unequivocally assigned by the chemical shift and the coupling constants of the CHX proton[']. In contrast, the mobility of the
C4-bridge in the bicyclo[4.2.l]nonane system leads to almost
identical multiplicities of the CHX protons in the NMR
spectra of the 5-endo- and 5-e~o-cornpounds~~~.
Comparison
of the CHX signals of (S) and of the endo-2-chlorobicyclo[4.2.l]nonane (7) obtained from (6)16] (Table 1) showed
that (5) is most probably the endo isomer.
Experimental
Synthesis of (11): A suspension of PdC12 (50 mg, 0.28
mmol), anhydrous CuCI, (2.7 g, 20 mmol) and sodium acetate (800 mg, 10 mmol) in glacial acetic acid (25 ml) is
treated with (1Oa) (1.36 g, 10 mmol) and the stirred mixture
is warmed to 70 "C for 1 h. After addition of 25 ml of water
the mixture is cooled and extracted with pentane (4 x 15 ml).
The combined pentane extracts are washed until neutral
(1 x NaHC03/H20, 1 x NaCl/H,O) and dried over MgS04.
After removal of solvent in a rotary evaporator the crude
product is distilled in vacuo (bulb-to-bulb, 80 "C/lO torr);
yield 1.5 g (77%) (i'l)[''l.
Received: July 16. 1979 [Z 316a IE]
German version: Angew. Chem. 91, 924 (1979)
CAS Registry numbers:
(I), 694-91-7; (2), 35406-02-1; (3), 71887-53-1: (41, 71887-54-2; (S), 71927-85-0
exo (6), 23890-32-6; endo (61, 25093-48-5; (7a), 71887-55-3; (76). 71962-06-6;
/lOa), 1004-84-8; (lob). 33383-06-1; ( 1 1 ) . 71 887-56-4: (Xa), 53433-66-2; (8b),
53433-69-5
[I] Review: J. Smidr, W Hafner, R. Jira, R. Sieber, J. Sedlmeier, A . Sabel, Angew. Chem. 74, 93 (1962); Angew. Chem. Int. Ed. Engl. 1, 80 (1962).
[2] Reviews: P. M. Henry. Adv. Organomet. Chem. 7 3 , 363 (1975): B. M. Trust,
Tetrahedron 33, 2615 (1977).
[3] a) W C. Baird, Jr., J. Org. Chem. 31, 2411 (1966); R. Baker. D. E. Halliday,
J . Chem. SOC.Perkin Trans. I1 IY74, 208; b) R. M. Giddings, D. Mutacker,
Tetrahedron Lett. 1978, 4077.
[41 A. Heumann, B. WaegeN, Nouv. J. Chim. I, 277 (1977).
IS] A . Heumunn, M. Reglier, B. WaegeN, Angew. Chem. 91, 925 (1979); Angew.
Chem. Int. Ed. Engl. 18, 867 (1979).
[61 C. Lame, A. Thuillier, C. R. Acad. Sci. C 273, 1258 (1971).
[7] (7a): IR (CHCII): 1735 cm-': 'H-NMR (CDC13): 6=4.17 (s, 2-H), 4.26 (m,
5-H). 2.04 ( s , CH,), 0.75 (21. 9-H "endo", J, = 14 Hz); (7b): 1R (CHC13):
1725 cm I ; 'H-NMR (CDC13): 6=4.37 (s, 2-H), 4.40 (m. 5-H), 2.04 (s,
CH,).
[8] A. Nickon, H . R. Kwasnik, C. T. Mathew. T D. Swartz, R. 0. Williams,J. B.
Digiurgro, J. Org. Chem. 43. 3904 (1978). We thank Professor A. Nickon,
The Johns Hopkins University of Baltimore, for the IR- and NMR spectra
of 2-brendanone.
[9] The corresponding acetate is well known: R. S.Bly, R. K. Bly, G. B. Kunizer,
S.P. Jmdal, J. Am. Chem. Sac. Y8, 2953 (1976).
[lo] W. T. Wipke. G. L. Goeke, J. Am. Chem. SOC.96, 4244 (1974).
[II ] ( 1 1 ) : 1R (Film): 3020.3000. 1440 (C-~C), 1720 (C--O), 1250 cm-' (C 0 ) ;
'H-NMR (CDCII): 6=4.86 ( J , = 8 , J2=4, J3=4 Hz, 1 H), 2.04 (s, 3H), 1.6
( s , 3H), 0.8-2.9 (m. I 1 H); "C-NMR (CDCI,): 6=171.2 (C), 135.3 ( C ) ,
125.0 (C), 79.3 (CHI. 53.1 (CH), 43.7 (CHZ), 32.8 (CH,), 26.6 (CH,), 26.0
(CHI), 25.8 (CHZ),21.3 (CH3). 13.1 (CH?); MS: m/e=134 (M-60, 100%).
Mechanistic Aspects of the Palladium-Catalyzed
Cyclization of 5-Methylenecyclooctene[**l
By Andreas Heumann, Marius Reglier, and Bernard Waegell['l
C1
I31
121
ill
OAc
OAc
OAc
141
151
Table I . Characteristic spectral data of the compounds (1)-(5) and (7). 'HNMR in CDC13, IR in CHCI,.
(11, 'H-NMR: S=4.79 (s, 2H, C=CH2), 5.56-5.72
(m. 2H, CH -=CH)
(2). 'H-NMR: 6=4.24 (m. J , = 4 , J 2 = 8 , J 3 = 1 4 H z , l H , CHCI)
(31, IR: 1720 cm-'; 'H-NMR: 6=4.24 (m. J,=4.5, J Z = 9 . J3=13 Hz, 1 H,
CHCI), 1.96 (s, 3H, OAc)
f4), IR: 1720 cm-'; 'H-NMR: 6=5.48-5.82 (m, 2H, CH=CH), 1.98 (s, 3H,
OAc)
(51, IR: 1730cm-'; 'H-NMR: 6=4.04(d,t, J , = J 2 = 4 . 5 , J , = 9 H z , l H , CHCI),
1.98 (s, 3H, OAc)
(71, 'H-NMR: 6=4.05 (d, I, J,=J2=4.5, J 3 = 9 Hz, 1 H, CHCI)
OH
171
The reaction of (1) reveals the paramount importance of
the reactivity of the C--Pd bond. In the reaction of (I) with
PdC12(PhCN)2 in benzene we were able to isolate the u-?T
complex (9) by simple filtration and oxidatively cyclize it to
the products (2)-(S).
From the structure of (9) one could expect during the cyclization step a reaction behavior similar to that of the corre-
The palladium-catalyzed cyclization of diolefins represents a simple and direct method for the preparation of substituted bi- and poly-cyclic systems[']. We report here on a
further reaction of this kind, the cyclization of S-methylenecyclooctene (I), which is readily accessible in four steps from
1,5-cyclooctadiene. Cyclization of (1) in the presence of
4
[*I Prof. Dr. B. Waegell, Dr. A. Heumann, DipL-Chem. M. Reglier
Laboratoire de Stereochimie associe au CNRS
Universite d'Aix-Marseille
Centre de St-JerBme, F-13 013 Marseille (France)
[**I This work was supported by the Delegation Generale a la Recherche Scientifique et Technique ( D G R S T decision d'aide n" 77.7.0755). We are grateful to
Huls, Marl, for supplying the I .5-cyclooctadiene.
Angew. Chem. Int. Ed. Enxi. I N (1979) No. I 1
0 Verlag Chemie, GmbH, 6940 Weinheim, 1979
'
0570-0833/79/llll-0867
1121
$ 02.50/0
867
Документ
Категория
Без категории
Просмотров
1
Размер файла
212 Кб
Теги
oxidation, cyclic, palladium, system, diolefins, catalyzed
1/--страниц
Пожаловаться на содержимое документа