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New Arene(dicarbonyl)chromium Chelates Application to Asymmetric Synthesis of Amines.

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Table 1. Product distribution from reactions of arenes with ground state oxygen atoms produced by microwave discharge Of 02/He.
Substrate
bl
6
Relative
rate [el
Relative yields of products [%] derived from
Substituent
methyl shift
methyl oxIdation
cleavage
oxidation of an aromatic
CH bond
SHzOH
CHO
Ial
"'I
1.0
1.3
orrho
meta
par0
71
7
orrho
mem
59
IS
21
wra
1
16
5
OClf,
b
Ihl
65
1
3.7
15
19
OH
CHO
lb,ci
28.5
92
3.5
&40
.
CHO
5.0
[a] At -78 "C. [b] At -30°C. [c] Also done by microwave discharge of N,0/N2. [d] At -25 "C. [el For ring substitution.
phase reaction of the rearranged phenols and of benzylic oxidation products151.
Oxidation of naphthalene in solution with
ground state oxygen atoms gave a- and @-naphtholsin 7: 1
ratio. The corresponding acetates were obtained in the same
ratio when the reaction was performed in acetic anhydride in
the presence of traces of sulfuric acid.
Experimental
Oxidation of naphthalene: A steady flow of O2and He (0.7
I/min, 7: 1 ratio) at 4 torr was passed through a quartz Utube containing a magnetically stirred methyl caproate solution of naphthalene (1 g in 5 ml). The side arm of the U-tube
was connected by a gas discharge cavity to the microwave
generator (Kiva MPG-2, 2450 MHz, 100 watt), which was
placed 5 cm above the substrate surface. After reaction for 1
h at 5 "C the material was chromatographed on silica gel to
give 600 mg starting compound, 280 mg of a-naphthol, 40
mg of P-naphthol, and small amounts of other oxidation
products.
Received: July 30, 1980 [ Z 622 IE]
German version: Angew. Chem. 92, 1037 (1980)
CAS Registry numbers:
Naphthalene, 91 -20-3; a-naphthol, 90-15-3; P-naphthol, 135-19-3; methylbenzene, 108-88-3; tert-butylbenzene, 9806-6; methoxybenzene, 100-66-3; 1,3,5-trimethylbenzene, 108-67-8; 1.2-dimethylbenzene, 9547-6; 1,3-dimethylbenzene,
108-38-3; o-methylphenol, 9548-7; m-methylphenol, 108-394; p-methylpbenol,
1 0 6 4 4 5 : o-;err-butylphenol, 88-18-6; m-(err-butylphenol, 585-34-2; p-Iert-bu(ylphenol, 98-54-4; o-methoxyphenol, 90-05-1; m-methoxyphenol, 150-19-6; p-methoxyphenol, 150-76-5; 2.4,6-tnmethylphenol, 527-60-6; 2,3-dimethylphenol,
526-75-0; 3.4-dimethylpheno1, 95-65-8; 2,6-dimethylphenol, 576-26-1; 2.4-dimethylphenol, 105-67-9; 3,5-dimethylphenol. 108-68-9; phenol, 108-95-2; 2,3,5-tnmethylphenol, 697-82-5; 2,5-dimethylphenol, 95.874; benzaldehyde, 100-52-7;
benzyl alcohol, 100-51-6; 3,5-dimethylbenzaldehyde,5779-95-3; 2-methylbenzaldehyde, 529-20-4; 3-methylbenzyl alcohol, 587-03-1; 3-methylbenzaldehyde,
620-23-5; oxygen atom, 17778-80-2
Angew. Chem. Inl. Ed Engl. 19 (1980) No. 12
@
E. Zadok, D. Amar, Y. Marur, J. Am. Chem. SOC.102, 6369 (1980).
R. Ilo, T. Migita, N . Monkawu, 0. Simamura, Tetrahedron 21, 955 (1965).
E. Grouenstein, A. Mosher, J. Am. Chem. SOC.92, 3810 (1970).
For other gas-phase oxidations of aromatic compounds, see: R. A. Bonanno,
P. Kim. J. Lee, S. R. Timmons, J . Chem. Phys. 57. 1377 (1972); T. M. Sloane.
ibid. 67, 2267 (1977); J. S. Gaffney. R. Artkinson, J. N. Pitrs. 1. Am. Chem.
Soc. 98, 1828 (1976); G. Boocock, R. J. Cvetanouii, Can. 1. Chem. 39, 2436
(1961); G. R. H. Jones, R. J. Cvetanouii, ibid. 39, 2444 (1961).
[S] Comparison of our results with those recently published by Takamuku. Sakurai et ul. (A. Hori, H. Matsumolo, S. Takamuku, H. Sakurai, J . chem. SOC.
Chem. Commun. 1978, 16 and Chem. Lett. 467 (1978); S. Takamuku, H.
Mutsumoto, A. Hori. H. Sakurar, J. Am. Chem. SOC.102. 1441 (1980)).on the
reaction of ground stale oxygen atoms producted by 7-radiolysis of liquid
CO2, shows considerable differences in the relative distribution of the oxidation products 7-Radiolysis leads to comparatively small yields of o-phenols
and complete lack of substituent cleavage products.
[l]
121
[3]
141
New Arene(dicarbony1)chromium Chelates:
Application to Asymmetric Synthesis of Amines
By Arleite Solladie-Cavallo, Jean Sufferi, and
Jean-Luc Haesslein"'
We have found that arene(dicarbony1)chromium chelates
(la-d) (synthetized by irradiation of arene(tricarbony1)chromium complexes (3a-d) (Scheme 1) undergo, with
alkyllithium compounds, nucleophilic addition on the azomethine carbon; hydrolysis of the intermediates then leads in
good yields to the chiral amines (2) (Table 1).
[*] Dr. A. Solladie-Cavallo. J. Suffert, J. L. Haesslein
Laboratoire de Chimie Organique de I'Ecole Nationale Supeneure de C h m ie, ERA du C.N.R.S., n" 687
Universite Louis Pasteur
P.O. Box 296/R8, F-67008 Strasbourg (France)
Verlag Chemie, GmbH. 6940 Wernheim, 1980
0S70-0833/80/1212-100S
$
. 02.50/0
1005
( f a ,b), n
=
I
1,2
OC)
MeLl
RL
Ph-C Hz-( C Hz),-C R-NHPh
Ph-(C Hz)2-NI-C H-Me
I
I
Ph
Ph
( h ) , n = 1, R = M e
(203, n = 1, R = nBu
(2h), n = 2, R = M e
(2Cl
Table 1. Reaction conditions and yields of reactions of ( 1 ) with alkyllithium
compounds.
Reactant
(Chelate)
R in
RLi
Reaction conditions
T["Cl
f [hl
0
- 30
0
50
0
0
0
-20
16
15
15
10
16
16
16
24
Yield
L96l
work-up (H,O/NH,CI), leading to the racemic amines (2ac) which are purified by chromatography and identified by
elemental analysis, mass spectra, IR, and 'H-NMR (Table
2).
Chemical yields depend on reaction temperature but the
absence of reaction with 2-lithio-1,3-dithiane may be ascribed mainly to steric hindrance.
When the optically pure chelate (IS)-(ld)"l is used (Scheme I), the amine (2d) obtained is up to 94% optically pure.
Nucleophilic addition of alkyllithium compounds to the optically pure arene(tricarbony1)chromium complexe (1 S)-(3d)
proceeds without asymmetric induction.
The new chelates (1) are good precursors of the chiral amines (2); replacement of the phenyl groups on the azine methine function by alkyl groups or hydrogen should provide
an efficient route to a large number of chiral amines.
Received: November 14, 1979 [Z 623 IE]
German version: Angew. Chem. 92, 1038 (1980)
Product
(Amine)
[I] (1 S)-fld) was synthesized from (IS)-( +)-tricarbonyl(o-methylbenzaldehydato)chromium; A. So/ladie-Caual/o, G. Solladie, E. Tsamo. J. Org. Chem. 44,
4189 (1979).
98
40
0
0
60
88
98
72
[a] [a]:"= -8.6 (c=O.4; CHCI,); optical purity 7796, calculated with [a]2:)(max)
= 11.2. [b] [a]:"=- 10.5 (crO.4; CHCI,); optical purity 94%. calculated as in
la]-
*
A benzene solution of the chelate (1) is added dropwise,
under argon, to a diethyl ether solution of the alkyllithium
compound (see Table 1). Decomplexation occurs during
Phosphorus Triiodide and Diphosphorus Tetraiodide,
New Reagents for Deprotecting Acetals and
Ketals1**]
By Jean-Noel Denis and Alain Kriefi')
On continuing our investigations on the reactivity of PI3
and Pz14 towards organic molecules[i1,we found that these
reagents allow the transformation of ketals into aldehydes or
ketonesf'l. Only few nonaqueous deprotections have so far
been reported for these protecting
Table 2. Selected physical and spectroscopic data of the chiral amines (20-d).
IR in CHCI,, 'H-NMR in CDCIdTMS.
( 2 ~ ) :m. p. 89 "C; IR: 3420 (NH). 3050-3000 (CH arom.), 2930-2850 cm - '
(CH2); 'H-NMR: 6 = 1.65 (s, CH,), 1.80-2.80 (m, (Cff2)z), 3.95 fs. NH),
6.10-7.60 (m, 15H. arom.)
(2a'): IR: 3420 (NH), 3060-3010 (CH arom.). 2930-2860 cm ' (CH'); 'HNMR: S=0.5-2.70 (m, (CH2)' und C,Hu), 3.93 (s, NH), 6.10-7.70 (m.
15 H, arom.)
(2b): IR: 3420 (NH), 3060-3020 (CH arom.), 2930, 2860 cm ' (CH2), ' H NMR: 6= 1.57 (s. CHI), 1.4-3.0 (m. (CH2),), 3.97 (s, NH), 6.10-7.60 (m.
15H, arom.)
(2c): IR: 3400 (NH), 3060-3040 (CH arom.), 2960-2900 c m - ' (CH2); 'HNMR: 6= 1.35 (d, CH,), 2.12 (s, NH), 2.70 (br. (Cff2)2),3.70 (4, CH-N),
6.90-7.30 (m. IOH, arom.)
( 2 4 : IR: 3415 (NH), 3050-3000 (CH arom.), 2935-2870 cm
(CH,), 'HNMR: 6= 1.66 (s, CH,), 1.98 (s, CH3), 1.90-2.80 (m. (CH2)'), 3.95 (s,
NH), 6.10-7.60 (m, 15H. arom.)
Table 1 Yields and conditions for reaction of aldehydes and ketones wlth P214
(method A) or PII (method B).
~
R'
R'
R'
Yield
["ml [a1
Method
91
85
63
60
64
57
78
81
67
75
65
85
79
65
58
A
B
A
B
A
B
A
B
A
B
A
A
B
A
B
T
["Cl
I
20
20
20
20
20
20
20
20
20
20
20
60
60
60
60
02
02
02
02
0 2 [b]
0 2 [b]
025
025
0 25 [c]
0 2 5 [c]
0 3 [d]
4
4
6
4
[hl
[a] Yields of purified products. [b] Reactions were conducted in the presence of
propene, giving a 10% increase in the yield of carbonyl compound. [c] This ketone contains I5% of an unidentifed product; it is absent if the reaction 1s conducted with an excess of P214 (0.55 mol) or PI, (1.1 mol) per mol of ketal. The ketone is thus formed in 79 and 77% yield respectively after stirring at (20"C, 15
min) [d] 0.92 rnol of ethyl iodide is formed per rnol of ketal.
Scheme 1. a) hu/benzene; b) RLi, - 20 "C; c) H20/NH,CI; d) hv/02; e) chromatography. ee = enantiomeric excess.
1006
0 Verlag Chemie, GmbH, 6940 Weinherm, 1980
['I DiplLChem. J . N. Denis, Prof. Dr. A. Krief
Departement de Chimie, Facultes Universitaires N. D. de la Paix
61, rue de Bruxelles, 8-5000 Namur (Belgium)
[**I The authors acknowledge award of a fellowship by Roussel Uclaf Company
(France) to J. N. D. and financial support of this work by FNRS.
0570-0(133/80/1212-1006
$ 02 50/0
Angew. Chem. Inf. Ed. Engl. 19 (1980) No. I 2
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