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Asymmetric Photocycloadditions with Optically Pure Spirocyclic Enones.

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H. Stetter, R. Y. Ramsch, H. Kuhlmann, Synthesis 1976. 733: H. Stetter.
G. DBmbkes, ibid. 1977. 403; 1980. 309.
iI.
'
,
El
meso- and D,L-form of bis(endo-bicyclo[2.2.1 jhept-5-en-2-yl)ethanedione
5a: 'H-NMR (80 MHz, CDCI,): S= 1.38 ( m ; 7-H,,, 7-Hh, 3-H.,), 1.75 (m:
3-H,), 2.90 (m: 4-H), 3.19 (m; I-H), 3.65 (m; 2-H), 5.73 ( m ; 6-H), 6.20
(m: 5-H). 40 :60 mixture of endo- and exo-l-(bicyclo[2.2. Ijhept-S-en-2yl)-1,2-propanedione 5b: 'H-NMR (80 MHz, CDCI,): 6= 1.2-1.6 (m:
endo: 3'-H,, 7'-H,,, 7'-Hh; exo: 3'-H,, 7'-H.,, 7'-Hh), 1.7-2.1 ( m ; endo: 3'H,; exo: 3'-H,), 2.33 (s; endo: CHI), 2.37 (5; exo: CH2), 2.9-3.2 ( m ;
endo: 4'-H: exo: I'-H, 2'-H,, 4'-H), 3.30 (bs; endo: 1'-H), 3.5-3.8 (dt:
endo: 2'-H,), 5.8 (dd; endo: 6'-H), 6.2-64 (m: endo: 5'-H; exo: 5'-H, 6'H).
171 1 was hydrogenated (Pd/C) to the 3,4-hexanedione, which was identical
with authentic material. I : 'H-NMR (80 MHz, CDCI?): 6=6.0-7.2
(ABC-m; 6 H , vinyl-H). "C-NMR (CDCII): S= 130.1 (d; <'-2, C-5),
133.0 (t: C-I, C-6), 189.0 (s; C-3, C-4). IR (film): C = 1690 c m - ' (C=O).
UV (acetonitrile): 1 = 4 3 4 ( E = 19).-2: 'H-NMR (80 MHz. CDCI,):
6=6.0-7.3 (ABC-m; 3 H , vinyl-H), 2.47 (s; 3 H , CH,). "C-NMR
(CDCII): S=24.2 (4: C-I), 128.7 (d: C-4), 133 I ( t ; C-S), 186.8 (s; C-3).
197.9 (s: C-2). IR (film): G = 1715 (C=O), 1690 (C=O) c m - ' . U V (acetonitrile): A=436 ( ~ ~ 2 0 ) .
[S] M. J. S. Dewar, W. Thiel. J. Am. Chem. Suc. 99 (1977) 4899. 4907.
191 R. C. Bingham, M. J . S. Dewar, D. H. Lo, J. Am. Chem. Soc. 97 (1975)
1285.
[lo] L. Asbrink, C. Fridh, E. Lindholm, Chem. P h m Lett. 52 (1977) 63, 69,
72.
[ I I ] T. A. Koopmans, Physika I(1933) 104.
[I21 D. Dougheny, P. Brint, S. P. McClynn, J . Am. Chem. Soc. IOU (1978)
5597.
i
I
I
Fig. 2. He(l(i)-photoelectron spectra of 1 (top) and 2 (bottom).
Table I . Ionization energies I";eV (error k0.03 ev) of 1 and 2. Assignments according to MNDO, M l N D 0 / 3 , and HAM/3. CO-CO torsion angle
always 165". A: Vinyl-CO torsion angle: A O", B optimized. Other parameters MNDO- and MIND0/3-optimized; HAM/3 calculations with MNDOoptimized parameters.
'7
MNDO MNDO MlND0/3
A
B
A
M I N D 0 1 3 HAM/3
B
A
HAM13
B [a1
11.25 n
10.28
10.67
10.68
12.47
10.28
10.72
10.73
12.48
8.99
10.60
10.63
11.30
8.99
10.60
10.63
11.30
9.23
10.16
10.19
11.13
9.29
10.16
10.28
11.29
2
9.42 n ,
10.78 x
11.32 n .
10.28
10.72
12.37
10.28
10.72
12.37
9.09
10.66
11.23
9.11
10.63
11.23
9.33
10.34
11.15
9.33
10.34
11.15
I
1
9.33 n ,
10.78 n
[a] In the case of I , vinylLC0 torsion angle 51 ".
Experimental
5a and 5b were pyrolized at 600°C and 0.01 to 0.02 torr in a gas-phase pyrolysis apparatus (small tube furnace fitted with quartz tube and directly coupled to four cooling traps). The cooling traps directly adjacent to the furnace,
and in which the products were collected, were cooled to -78°C (1st trap)
and - 178°C (2nd trap), respectively. The storage vessel for 5 was heated to
I lo'<' i n the case of Sa, and to 60°C in the case of 5b. After ca. 2 h, there
was no longer any starting compound 5 in the storage vessel: the first cooling trap contained the dione 1 (81%) o r 2 (89%), the second trap cyclopentadiene.
Asymmetric Photocycloadditions with
Optically Pure, Spirocyclic Enones.
Simple Synthesis of ( + )- and ( - )-Grandis01
By Martin Demuth,* Albert Palomer.
Heinz-Dieter Sluma, Ashesh K . Dey, Carl Kruger, and
Yi-Hung Tsay
+
Photochemical [2 2]-cycloadditions of enones and related chromophores to olefins have previously been the
subject of numerous investigations from the standpoint of
asymmetric induction."' In more recent studies of such cycloadditions based on a principle that has also been tested
by us, enonesI'l or compounds with enone-like photoreactive moietiesl3I have been used which contain a chiral auxiliary group. After the cycloaddition the chiral auxiliary
group is split off and can thus be recovered. The aim of
our present investigation was to prepare an enone moiety
in the simplest way from readily accessible materials and
to couple it rigidly, i.e. spirocyclically, to the auxiliary material (novel principle of stereofacial differentiation) and
to recover this under mild conditions after the cycloaddition (avoidance of isomerizations). The dioxacyclohexenones (-)-2 and (-)-3 have proven suitable for this strategy (Fig.
Received: June 6, 1986 [Z 1809 I€]
German version: Angew. Chem. 98 (1986) 1134
CAS Registry numbers:
1, 104910-78-3; 2 , 91238-45-8; 5a, 74895-76-4; 5b, 104910-80-7
0
(-1-2
(-1-3
Fig. I . Olefins add a-srlrctibrly to the dioxacyclohrxrnones (-)-Z and ( - ) - 3 .
[ I ] R. kaksson, T. Liljefors, J . Chem. Soc. Perkin Trans. 2 1983. 1351.
121 P. L. Verheijdt, H. Cerfontain, J. Chem. Soc. Perkin Trans. 2 1982.
1541.
131 a) S L. T. Thuan, J. Wieman, C. R. Hebd. Seances Acad. Sci. Ser. C272
(1971) 233; b) P. B. Shepson, E. 0. Edney, E. W. Corse, J. Phys. Chem.
88(1984)4122.
[41 R. Albert, C . Heller, R. Iden, G. Martin, H.-D. Martin, B. Mayer, A.
'
Oftring, Isr. J . Chem. 25 (1985) 74.
Anyrw
Chem. In,. Ed. Engl. 25 (1986) No. I2
[*] Prw-Doz. Dr M. Demuth, DipLChem. A. Palomer,
Dr. H.-D. Sluma, Dr. A. K. Dey
Max-Planck-fnstitut fur Strahlenchemie
Stiftstrasse 34-36, D-4330 Mulheim a. d. Ruhr (FRG)
Prof. Dr. C. Kruger, Dr. Y.-H. Tsay (X-ray structure analysis)
Max-Planck-lnstitut fiir Kohlenforschung
Kaiser-Wilhelm-Platz I, D-4330 Mulheim a. d. Ruhr (FRG)
0 VCH Ver1agsge.rellschafi mhH. 0-6940 Weinheirn. 1986
0570-0833/86/1212-1117 $ 02.50/0
1117
A mixture of ( - ) - 2 and ( - ) - 3 can be obtained via two
routes: By rearrangement of the dioxacyclohexadione l C 5 l
after acetylation (acetyl chloride, pyridine; analogously as
in Ref. [6]) into a 1 : 1 mixture of ( - ) - 2 and ( - ) - 3 (diglyme, 120°C, analogously as in Ref. [7]) (Scheme I , Route
I ; ca. 10% yield) or in one step by condensation of (-)menthone, (-)-4, with tert-butyl acetoacetate in acetic anhydride in presence of sulfuric acid (Scheme 1, Route 11;
ca. 34% yield). The ratio in which the two isomers are
formed can be varied: At -5"C, ( - ) - 2 and ( - ) - 3 are
formed in the ratio 6 : I , at 10°C in the ratio 1 : 1.
The photocycloadditions of ( - ) - 2 and (-)-3['] with the
olefins listed in Table 1 (quartz vessel, medium-pressure
mercury lamp) yielded products[91which are cis,anti,cisconfigurated at the new coupling sites (Table 2, experiments I, 3 , and 4).""l The pronounced regioselectivity in
additions with methylcyclobutene (experiments 1 and 4 at
- 78 " C ) decreases on using an acyclic olefin (experiment 2
at -78°C). The consistently high stereoselectivity (see a : b
values in Table 2) lends support to the soundness of the
spiro principle for stereofacial differentiation. Whereas a
low reaction temperature is essential for a preparatively interesting stereoselectivity in the case of reactions 1, 2, and
4, considerable induction is already achieved at 5°C with
Table 2. Results of the reactions listed in Table I .
no+
0
Expt.
(-)-2/3
1
7-
Yield
["Cl
P o l la1
P + P'
I
2
3
- 78
+ 20
- 78
+ 20
- 40
+ 5
- 78
20
55 (70)
Icl
33 (48)
Icl
70 (82)
64 (81)
56 (72)
icl
Regioselectivity
P:P'
7:l
1 : l
3 : l
1:I
-
7:l
Stereoselectivity [b]
a . b
5:l
1 : l
8.1
2.5 : 1
10 : 1
9:l
5:l
1 : 1
(-1-4
4
Scheme I
[a1 Purity of P and P>96%: crude yields of all cycloadducts in brackets. [b]
Corresponds to the facial selectivity (see Fig. I): cf. also footnote [b] ofTable
I. [c] Preparatively uninteresting yields.
The products could be separated cleanly and easily by
crystallization of (-)-3 from n-hexane at -10°C and
chromatography of the filtrate on silica gel [(-)-Z]. The
yields quoted for Routes I and I1 are the sum of the yields
of pure (-)-Z and ( - ) - 3 . The spectroscopic data are collected in Table 3.
+
1:l
Table 3. Spectroscopic data of the compounds ( - ) - 2 , ( - ) - 3 , ( + ) - 5 , and
i n n-hexane: ' H - N M R : 400 MHz, CDC13; "CN M R . 100.6 MHz, CDCI,. The optical rotations were measured in CHCI, at
23°C (c [g/IOO mL]) and converted to specific rotation values [a],,.All the
compounds gave correct elemental analyses.
( + ) - 8 . IR in CHCI,: UV
( - ) - 2 : IR: ?= 1710, 1630, 1225, 1180, 1140, 1075 c m - ' : MS: m/z 238 ( M e ) ,
Table I . Photocycloadditions of the dioxacyclohexenones ( - ) - 2 and ( - ) - 3
with olefins [a]. The spectroscopic data of the products ( + ) - 5 and ( + ) - 8 are
given in Table 3.
Expt.
Dioxacyclohexenone
I
(-1-2
Olefin
Photoproducts [b, c] [9]
P'
P
196, 154, 139, 112(100%),69,55,41; UV:dm.,,(&)=244nm(5992); 'H-NMR:
6=5.12(s,lH),2.56(ddd,5=2.5,3.5,and 13.5Hz,lH),ca.2.17(dsept,
J = 2 . 5 a n d 7 H z , IH), 1.94(s,3H),1.42-1.80(m,6H),0.97(t,J=13Hz,
IH),
0.91 (d, J = 7 Hz, 3H), 0.87 (d, 5-7 Hz, 3H), 0.84 (d, 5=6 Hz, 3H); " C NMR: 6= 168.65 (s), 161.04 ( s ) , 109.75 (s), 93.12 (d), 49.39 (d), 40.98 (t), 34.08
(t), 28.58 (d), 25.55 (d), 23.19 (q), 22.22 (t), 21.58 (q), 20.07 (4). 18.48 (4);
[air,= -27.4' (0.48)
( - 1-3. single-crystal X-ray structure analysis (cf. Fig. 2); m.p. = 49-51 "C:
IR: G 1 7 1 0 , 1630, 1275, 1210, 1095, 1075 c m - ' ; MS: cf. ( - ) - 2 : UV:
d,,,(&)=241 nm (5760); 'H-NMR: 6=5.16 ( s , 1 H), 2.57 (ddd, J = I, 2, and
14 Hz, I H), ca. 2.29 (d sept, J = 1 and 7 Hz, I H), 1.95 ( s , 3 H), ca. 1.74 (dm,
J = 13.2 Hz, I H), ca. 1.65 (m. 1 H), 1.44-1.56 (rn, 4H), 1.05 (t, J = 13.2 Hz,
I HI, 0.90 (d, J = 7 Hz, 3H), 0.85 (d, J = 7 Hz, 3H), 0.83 ( i ,J = 7 Hz, 3 H ) ;
"C-NMR: 6 = 168.01 (s), 161.5 (s), 109.44 ( s ) , 93.69 (d), 49.19 (d), 40.52 (t),
33.87 (1). 29.65 (d), 25.0 (d), 23.08 (q), 21.78 (t), 21.54 (q), 20.02 (q), 18.1 1 ( q ) ;
[a]n= -22.5" (0.4)
( + ) - 5 : single-crystal X-ray structure analysis;
G = 1710, 1260,915 c m - ' : MS: m/z 306 ( M e ) , 239,
'H-NMR: 6=3.05 (s, 1 H), ca. 2.41 (d sept, J=2.5
(m, SH), 1.93 (ddd, J=2.5, 6, and 13 Hz, IH), 1.55
0
m.p.= 101-103°C: IR:
155, 124, 109 (lOO%), 84:
and 7 Hz, I H), 1.8-2.45
( s , 3H), 1.2-1.8 (m, 6H),
I.3(t,J=l3Hz,IH),1.15(~,3H),0.91(d,J=7Hz,3H),0.87(d,5=6.5Hz,
3H), 0.85 (d, 5=7 Hz, 3H); "C-NMR: 6 = 168.29 (s), 107.59 (s), 76.38 (s),
51.61 (d), 50.08 (d), 49.50 (t). 48.14 (d), 42.22 (s), 35.22 (t), 33.87 (t), 29.28 (d),
24.32 (d), 23.50 (q). 23.40 (q), 22.09 (4). 21.29 (q), 21.0 (t), 18.08 (q). 17.22 (t);
[all,= +55.3" (1.2)
4
( + ) - 8 :single-crystal X-ray structure analysis: m.p. =98-1OO0C: IR: C= 1715,
1320 c m - ' . MS: m / z 306 ( M e ) , 239, 155, 124 (lOOo/~), 109, 84; 'H-NMR:
6=3.02(s, IH), 1.85-2.4(m,6H), 1.9(ddd,J=2.5,6.5,and12Hz,IH),l.2[a] Molar ratio dioxacyclohexenone :olefin= 1 :4; c(( - ) - 2 ) = c ( ( -)-3)=0.2
mol/L; experiments I. 2, 4 in n-hexane, experiment 3 in acetonitrile. [b] Besides the regioisomers P and P', small amounts of stereoisomers with complementary four-membered ring configurations are formed (cf. u : b values in
Table 2). [c] Pure products after column-chromatographic separation.
1118
0 V C H Verlugsgesellschufi mhH. 0-6940 Weinheim. 1986
1.75 (m, 7H), 1.49 (s, 3H). 1.13 ( s , 3H), 0.86 (d, J=7.5 Hz, 3H). 0.85 (d,
J = 6 . 5 Hz, 3 H), 0.84 (d, J-6.5 Hz, 3 H); "C-NMR: 6 = 168.69 (s), 109.07 (s),
77.0 (5). 51.34 (d), 51.26 (d), 48.1 1 (d), 46.76 (t), 42.26 ( s ) , 35.20 (I), 34.20 (1).
29.84(d), 25.01 (d), 23.54(q),22.44(q), 22.07 (t).21.30(q), 21.23 (q). 18.38(q),
17.29 (I); [a]"=+ 18.9" (0.52)
0570-0833/86/1212-1118 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 25 (1986) No. 12
cyclopentene. Since attack from the a-side is preferred to
the same extent in the case of ( - ) - 2 and ( - ) - 3 (experiments I and 4) they are suitable educts for selective entry
to complementary series of enantiomers without-as is
otherwise usual-the chiral auxiliary having to be changed
(see, e.g., I21).
The preferred addition of the olefins to the a-side of the
enones ( - ) - 2 and ( - ) - 3 rules out any effective shielding
by the isopropyl group, and is apparently determined conformationally. We presume that the dioxacyclohexenone
ring could adopt a twisted boat conformation in solution,
an arrangement that exposes the a-side and which has
been found X-ray crystallographically in crystalline ( - ) - 3
(Fig. 2).
c1
W
c5
C6
c14
2%
A,
Fig. 2. Crys!al structure of ( - 1 - 3 . a=9.283(1), b = 14.497(1), c=21.107(2)
V=2840.4A',p,,,,= 1.11 g cm-',p=0.72 cm-I, 2 = 8 , s p a c e g r o u p P2,2,2,,
6640 reflections, 3976 observed ( I > 2a(1)), 307 refined parameters,
R =0.056, R,=0.065. Further details of the crystal structure investigation are
available o n request from the Fachinformationszentrum Energie, Physik,
Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen2 (FRG), on quoting
the depository number CSD-51953, the names of the authors, and the full
citation o f the journal.
The value of the method presented here has been confirmed by the first example of its application (Scheme 2 ) .
The major product of experiment 1, ( + ) - 5 , was smoothly
hydrolyzed with formic acid to give (-)-4 and (-)-6["'l
(80% yield after column chromatography) without epimerization occurring at the acetyl group.iz1 (-)-6 was converted into (+)-grandisol, ( +)-7Ji'-i31
by a procedure already described in the l i t e r a t ~ r e . " ~A
" ~specific rotation of
[a][,=+20° was calculated for (+)-7 (c=0.3 g/100 mL, nhexane; corrected literature values: [a],,= 18.5"[""] and
19.6"'iih1). Thus, it has been possible for the first time to
+
+-
synthesize the boll weevil (Anthonornus grandis) pheromone in optically pure form. At the same time, this fivestep synthesis is the shortest sequence so far for the preparation of this highly active natural
the enantiomer of which, (-)-grandisol, can be obtained analogously from (+)-8.
Received: June 13, 1986;
revised: September I, 1986 [Z 1815 I E ]
German version: Angew. Chem. 98 (1986) 1093
[ I ] Review of photochemical [2+ 21-cycloadditions: A C. Weedon in W. M.
Horspool (Ed.): Synthetic Organic Photochemistrj~.Plenum, New York
1984, p. 61.
[2] A. I Meyers, S . A. Fleming, J Am. Chem. Soc. 108 (1986) 306.
131 G. L. Lange, C. Decicco, S. L. Tan, G. Chamberlain, Tetrahedron Lett.
26 (1985) 4707.
141 a) M. Demuth, A. Palorner, unpublished; b) M. Demuth, Pure Appl.
Chem. 58 (1986) 1233.
IS] Procedure: 1 : Condensation of ( - ) - 4 and tert-butyl acetoacetate in acetic anhydride, catalytic amounts of sulfuric acid, room temperature,
24 h. The sole, previously described analogous condensation of ( + )camphor with a-methylmalonic acid required 200 days: A. Michael. N.
Weiner, J . Chem. Soc. 58 (1936) 680: €3. Eistert, F. Geiss, Chem Ber Y4
(1961) 929.
[6] Y . Oikawa, K. Sugano, 0. Yonemitsu, J. Org. Chem. 43 (1978) 2087.
171 M. Sato, H. Ogasawara, K.Oi, T. Kato, Chem. Pharm. Bull. 31 (1983
1896.
181 D Seehach, J. Zimmermann, Helu. Chrm. Acta 69 (1986) 1147; we thank
Prof. D. Seebach (ETH Zurich) for sending his manuscript prior to puhlication.
[9] The analytical data for all the new products are consistent with the given
structures; see also Table 3.
1101 Cf. also investigations with an achiral, monocyclic dioxacyclohexenone:
a) S. W. Baldwin, J. M. Wilkinson, J . Am. Chem. Soc 102 (1980) 3634;
h) S. W. Baldwin, G . F. Martin, D. S . Nunn, J. Org. Chem. 50 (198s)
5720.
[ I I ] Syntheses of (+)- and (-)-grandis01 in optically enriched form: a ) P. D.
Hobbs, P. D. Magnus, J . Am. Chem. Soc. 98 (1976) 4594; b) K. Mori,
Tetrahedron 34 (1978) 915: c ) see also ref. [2].
[12J Structure: J. H. Tumlinson, R. C. Gueldner, D. D. Hardee. A. C.
Thompson, P. A. Hedin, J. P. Minyard, J . Org. Chem. 36 (1971) 2616.
1131 Syntheses of (+)-grandisol: a) K. Mori in J. ApSimon (Ed.): The Total
Synthesis OJ Natural Products. Voi. 4. Wiley-lnterscience, New York
198 1 ; b) G Quinkert, Synform 1983. I ; c) E. Negishi, L. D. Boordman, J.
M. Tour, H. Sawada, C. L. Rand, J. Am. Cliem. Soc. 105 (1983) 6346; d )
G. Rosin;. E. Marotta, M. Petrini, R. Ballini, Tefrahedron 4 / (1985)
4633.
[I41 For reference to a synthesis of (+)-grandis01 based on the use of d n
achiral monocyclic dioxacyclohexenone see: S. W. Baldwin i n A. Padwa
(Ed.): Organic Photochemistry. Yo/. 5. Dekker, New York 1981. p. 123.
Skeletal Rearrangements on Clusters:
The Reaction of [(rBuP)Fe,(CO),,I with
Diphenylacetylene* *
By Konrad Knoll, Gottfried Huttner,* Laszlo Zsolnai.
and OIli Orarna
p3-RP groups have proved useful as building blocks for
clusters. The metal atoms that they bridge are held together in the course of a reaction in such a way that the
mechanism of reactions that involve cleavage of metal-meta1 bonds can be studied in detail."-" This application of
[*I
M
1+)-5
H02C.
(-)-6
1+)-7
Schenic 2. Shortest synthehis of' ( + )-grandi>ol, ( + 1-7. reported so far. a)
HCOOH, H 2 0 / M e 2 C 0 ,40°C. 20 h. b) Me,SiCH,MgCI, tetrahydrofuran, reflux, SOCI,, room temperature: analogously as in [13d]. c) LiAIH,, Et,O,
room temperature: analogously as in [13d].
Angelc,. C'ltem. I n / . Ed. Enyl. 25 (19861 No. 12
Prof. Dr. G. Huttner ['I, Dipl.-Chem. K. Knoll,
Dr. L. Zsolnai, Doz. Dr. 0.Orarna
Lehrstuhl fur Synthetische Anorganische Chemie der Universitiit
Postfach 5560, D-7750 Konstanz (FRG)
['I
Present address:
lnstitut fur Anorganische Chemie der Universitat
Irn Neuenheimer Feld 270, D-6900 Heidelberg (FRG)
[**I This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chernischen Industrie. 0.0. thanks the Finnish Academy
of Sciences for a fellowship.
0 V C H Verlagsgesellscha/t m b H . 0-6940 Weinherm. 1986
0570-0833/86/1212-11l9 $ 02.50/0
1119
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