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Facile Entry to Geminally Dialkylated Chlorins.

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[ S ] A. Schmidpeter, A. Willhalm, Angew. Chem. 96 (1984) 901; Angew.
Chem. Inr. Ed. Engl. 23 (1984) 903: R. 0. Day, A. Willhalm, J. M.
Holmes, R. R. Holmes, A. Schmidpeter, ibid. 97 (1985) 775 and 24 (1985)
764.
191 Procedure. 7.CI: A yellow solution of 6.C1 (OAOg, 3 mmol) in ethanol
becomes hot and decolorizes within 10 min after addition of 0.60 mL of
30% hydrogen peroxide; at the same time, colorless crystalline 7 .CI precipitates. Yield: 0.83 g (93%), m.p. 194-196°C (dec.). "P{'H}-NMR
(DzO): 6 = - 3 ; "C{'H}-NMR (DzO, CDxCN): 6= 170 (d, ' J p r - = 139 Hz,
amidinio-C), 45 (d, 'JPc=2.8 Hz, CH,): 'H-NMR ( D 2 0 ) : 6=3.30
(CH3).
[I01 Colorless crystals from acetone, m.p. 224-226°C (dec.). Monoclinic, P2/c,
a = 10.419(2), b=6.958(2), c = 11.959(2)
105.24(2)", 2 = 2 , EnrafNonius CAD4 diffractometer, Mo,,. (graphite monochromator) for
2 " 5 2 8 5 0 " ; 1179 independent reflections with 1 > 2 a ( l ) ; R=0.064,
R , =0.094. Further details of the crystal structure investigation are
available o n request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen2, on quoting the depository number CSD-51800, the names of the authors, and
the full citation of the journal.
[ I l l The structure of the PO2 group compares with that in the bis(tetramethy1amidinio)diphosphonate:F. Sanz, J. J . Daly, J. Chem. SOC.Dalton Trans. 1972. 2267
A, a=
3 R'=Vinyl
R2=H
M = FeCl
[7]
4R'=H
R2=CH3
M=2H
Facile Entry to Geminally Dialkylated Chlorins"*
By Franz-Peter MontjortP and Gotgried Zimmermann
Dedicated to Professor Burchard Franck
on the occasion of his 60th birthday
Factor I 1 and sirohydrochlorin 2a are novel porphinoid pigments with a chlorin and isobacteriochlorin structure, respectively. Their reduced derivatives occur as intermediates in the biosynthesis of vitamin Blz via uroporphyrinogen III."l Iron-containing sirohydrochlorin 2b,
moreover, functions as prosthetic group in sulfite- and nitrite-reductases of bacteria and plants.[21
I
2a M = 2 H
2b M = F e
One of the main difficulties in modelf3] and total synof these structure types is the construction of the
geminally dialkylated moiety in the pyrrole rings A or A and
B. We have now found that this moiety can be conveniently constructed starting from the readily accessible hydroxyalkylporphyrins by Claisen rearrangement with N, Ndimethylacetamide dimethyl a ~ e t a 1 . I ~ ~
A 3-hydroxyethylporphyrin 5l6]suitable as starting compound can be obtained via deuteroporphyrin dimethyl es-
['I
[**I
458
Scheme I . Reaction conditions: a) CHIC(OCH,)2N(CH,)2,o-xylene, molecular sieve 3 A, argon, 160°C. 1 h: flash chromatography; crystallization 76%. b) Hz, Pd/C, CH30H. room temperature, 2 h: flash chromatography; crystallization 70%. - All the new compounds have been characterized by elemental
analyses and UV/VIS, 'H-NMR and mass spectroscopy. Selected spectroscopic data: 7 , UV/VIS (CHCI,): A,,,,, =399 n m (lgs=5.176), 496 (3.99). 503
(3.951, 532 (4.031, 602 (3.56). 629 ( 3 . 4 0 659 (4.61); 'H-NMR (CDC13, 270
M H z ) : 6=-2.68, -2.52 (2m, 2NH). 2.19 (5, 2-CH3), 2.82 (d, 5-7.5 Hz,
3'-CH,), 3.25 (AB system, 2-CH2),6.44 (q, J = 7 . 5 Hz, 3'-H), 8.86 (s, 20-H),
9.52 (s, 5-H): MS (200°C): m / z 651 (26%. M+), 565 (lOOo/o,
M'-CHKON(CHh).
6 , UV/VIS (CHCL): 1,,.,,=392 (lg~=5.195), 489
(4.025), 496 (4.041). 522 (3.1853, 532 (3.047), 592 (3.505), 616 (3.466), 645
(4.583); ' H - N M R (CDCI,, 270 MHz). 6 = 1.18 (t. 5 ~ 7 . 4Hz, CH,, 3-ethyl),
2.20 (5, 2-CH3), 2.42 (m, J=7.4 Hz, CHZ,3-ethyl), 3.25 (AB system, 2-CHZ),
4.66 (t, 3-H), 8.79 ( s , 20-H), 9.01 (s, 5H).
I
1
[*I
7
Prof. Dr. F.-P. Montforts, ['I Dr. G. Zimmermann
Institut fur Organische Chernie der Universitat
Niederurseler Hang, D-6000 Frankfurt am Main 50 (FRG)
Present address: FB-2-Chemie. Universitat Bremen, Loebenstr. NW2,
2800 Bremen 33 (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie. We thank Prof. Dr. D. Leibfritz
(Universitat Bremen) for recording the mass spectra.
0 VCH Verlagsgesellschafr mhH. 0-6940 Weinheim. 1986
ter 4"' from hemin hydrochloride 3 by a known pathway.
Upon reaction with N,N-dimethylacetamide dimethyl acetal, 5 is converted into 7 . The Z-configuration of the exocyclic double bond in the product 7, which is readily detectable by intramolecular 'H-nuclear Overhauser effect
(NOE), evidences the expected stereoselective course[81of
the rearrangement. Catalytic hydrogenation of 7 affords
the chlorin 6, whose cis-configuration likewise follows
from a NOE experiment (Scheme 1).
Since there are methods available for the efficient synthesis of porphyrins, and since hydroxyalkyl substituents
can be readily introduced by acylation with subsequent reduction, the concept presented here should open u p a
route to the natural products 1 and 2. Preliminary experiments show that hematoporphyrin dimethyl ester is converted by double Claisen rearrangement into the isobacteriochlorin structure type, but the stereochemistry involved
thereby i s complex and still requires clarification.
0570-0833/86/0505-0458
Received. December 20, 1985:
revised: February 6, 1986 [ Z 1598 IE]
German version' Angew Chem 98 (1986) 451
$
02.50/0
Angew. Chem. Int. Ed. Engl. 25 (1986) No. 5
CAS Registry numbers:
1, 73528-45-7; 2a, 65207.12-7; 5, 63148.21-0; 6 , 101544-05-2; 7, 101544-04-1;
MezNC(OMe)zMe, 18871-66-4.
[I] A. R. Battersby, E. McDonald in D. Dolphin (Ed.): Vifamin B,r. Vol. I ,
Wiley, New York 1982, p. 107.
121 a) L. M. Siegel, M. J . Murphy, H. Kamin, J . Biol. Chem. 248 (1973) 251;
b) M. J Murphy, L. M. Siegel, ibid. 248 (1973) 691 1; c) M. J. Murphy, L.
M. Siegel, H. Kamin, D. Rosenthal, ibid. 248 (1973) 2801; d ) M. J. Murphy, L. M. Siegel, S. R. Tove, H. Kamin, Proc. Narl. Acad. Sci. USA 71
(1974) 612.
[3] a) A. R. Battersby, L. A. Reiter, J . Chenz. SOC.Perkin Trans. I 1984. 2743;
b) A. R. Battersby, C. J. R. Fookes, R. J. Snow, ibid. 1984. 2725, 2733; c)
C . K . Chang. C . Sotiriou, J . Org. Chem. 50 (1985) 4889; d ) F.-P. Montforts, U. M. Schwartz, Liebigs Ann. Chem. 1985, 1228. This work contains
a complete list of references to corresponding model syntheses from the
laboratories of Eschenmoser and Bafrersby.
141 a) C. J. Dutton, C. J. R. Fookes, A. R. Battersby, J . Chem. SOC.Chem.
Commun. 1983. 1237; b) F.-P. Montforts, U. M. Schwartz, Angew. Chem.
97 (1985) 767; Angew. Chem. Inr. Ed. Engl. 24 (1985) 775; c) S. P. D.
Turner, M. H. Block, Z. C . Sheng, S. C. Zimmermann, A. R. Battersby, J.
Chem. Soc. Chem. Commun. 1985. 583; d) M. H. Block, S. C. Zimmermann, G. B. Henderson, S. P. D. Turner, S. W. Westwood, E J. Leeper, A.
R. Battersby, ibid. 1985, 1061.
[ S ] a) H. Meerwein, W. Florian, N. Schon, G. Stopp, Justus Liebigs Ann.
Chem. 641 (1961) 1 ; b) D. Felix, K. Gschwend-Steen, A. E. Wick, A. Eschenmoser, Hell'. Chim. A a a 52 (1969) 1030; c) A. E. Wick, D. Felix, K. Steen,
A. Eschenmoser, ibid. 47 (1964) 2425.
[61 a) H . Brockrnann jr., K. M. Bliesner, H. H. Inhoffen, Jusrus Liebigs Ann.
Chem. 718 (1968) 148; b) K. M. Smith, E. M. Fujinari, K. C. Langry, D.
W. Parish, H. D. Tabba, J. Am. Chem. SOC.105 (1983) 6638; c) P. S. Clezy, V. Diakiw, N. w . Webb, J . Chem. Sac. Chem. Commun. 1972, 413.
[71 R. K. DiNello, C . K. Chang in D. Dolphin (Ed.): The Porphyrins, Vol. I ,
Academic Press, New York 1978, p. 294.
181 R. K. Hill in J. D. Morrison (Ed.): Asymmetric Synfhesis. Val. 3, Purr B.
Academic Press, New York 1984, p. 503. On using enantiomerically pure
5 its chirality should be transferred to the geminally dialkylated center in
2
3
a
b
c
d
e
f
Et
Et
Et
Me
Me
Et
Ph
Ph
Me
Ph
Ph
Ph
Me
Ph
H
Me
Ph
H
Scheme I
thioaldehyde H-atom in the 'H-NMR spectra of 4c and 4f
(6>9; see Table 1). The position of the signal and the
magnitude of the coupling constants for the thiocarbonyl
C-atom in the I3C-NMR spectra of 4a (6=183.77; q,
'J=8.2 Hz), 4b (175.28, s), and 4f (163.86; d, ' J = 179 Hz)
Table 1. Melting points, assignment of configuration, and selected 'H-NMR
data of 4.
["Cl
Configuration
'H-NMR (CDCI,, 6 values)
NR'R'(alky1)
R'
a
110-1 11
E
b
127-128
E
c [bj
91-92
155-156
133-134
140-141
160-161
E
1.19 (t; 6 H )
3.43 (4 H) [a]
1.13 (1; 3 H)
1.26 (1; 3 H)
3.20-3.90 (m; 4 H )
3.40 (s; 3 H)
3.40 (s; 3 H)
3.39 (s: 3 H)
3.5 I (s; 3 H)
4
M.p.
I.
+
Thioketone S-Oxides by 12 21-Cycloaddition of
Ynamines to N-Sulfinyltosylamide
d [cl
By Steffen Kosack, Gerhard Himbert,* and Gerhard Maas
f [el
+
e
Z
2
Z Id1
Z
-
2.54 (s; 3 H)
7.40 ( m ; 3 H)
7.95 (m: 2 H )
9.39 (s: I H)
9.09 ( s ; 1 H)
2.21 (s: 3 H)
[dl
9.34 (5; 1 H)
Ynamines undergo [2 21-cycloaddition reactions with
compounds that contain electrophilic C = C double bonds
or carbonyl-, thiocarbonyl- or imino groups."' The resulting
cyclobutenes are, as a rule, stable"."
exception^'^^),
whereas the 1,2-dihydro-oxete, -thiete, and -azete derivatives that are formed initially isomerize by electrocyclic
ring-opening to give a,&unsaturated amides, thioamides,
and amidines, re~pectively.".~~
In continuation of our studies on cycloadditions we
have examined the reaction of ynamines la-f with N-sulfinyltosylamide 2.Is1We were able to isolate, in good yields (66go%), the a-amidinothioketone oxides 4 (Table 1),I6l whose
formation can be explained in terms of a spontaneous ring
opening of the 1,2-dihydro-1,2-thiazetederivatives 3
(Scheme I).
The constitution of the open-chain products 4 is substantiated, in particular, by their I R spectra; the N-sulfonylamide moiety is revealed by intense bands in the regions
1510-1560 cm-' ( C = N ) as well as 1270-1305 and 11391152 c m - ' (SO,), whereby the region of the asymmetric
SO2 valence vibration (C= 1300 crn - ') is especially characteri ~ t i c . " We
~ assign one of the intense absorptions between
1075 and 1139 c m - ' to the sulfinyl group.[81Confirmation
of the structure is provided by the chemical shift of the
[a] Unstructured broad signal. [b) The E isomer I S obtained upon addition of
l c t o 2 followed by rapid isolation; in solution, it transforms into the Z
isomer (e.g. in CDCI, at room temperature in ca. 1 h). [c] New signals
(6=2.27 and 3.43<40%) appear in the 'H-NMR spectrum within 5 h ; these
we assign to the E form. [d] Unequivocal assignment of configuration impossible owing to overlapping of the aryl-proton signals. [el The 'H-NMR spectra of some crystal fractions show a second, less intense singlet at 6 e 9 . 5 0 ,
which we assign to the E-form.
[*I
Fig. 1. ORTEP diagram of the crystal structure of 4b. The vibration-ellipsoids are drawn at the 50% probability level. Important bond lengths [A] and
angle ["I: S2-CI3 1.629(3), S2-03 1.470(4); C13-S2-03 115 7(2) [9].
Prof. Dr. G. Himbert, Dipl.-Chem. S. Kosack, Prof. Dr. G. Maas
Fachbereich Chemie der Universitat
Postfach 3049, D-6750 Kaiserslautern (FRG)
Angetr.. Chem. I n / . Ed. Engl. 25 (I986) No. 5
0 VCH Verlugsgesellschufr mbH. 0-6940 Weinheim, 1986
0570-0833/86/0505-0459 $ 02.50/0
459
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