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1 1- and 1 o-Dilithioallyl Phenyl Sulfone Synthesis Geminal Cycloalkylation and Lithium-Titanium Exchange.

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1,l- and 1,o-Dilithioallyl Phenyl Sulfone:
Synthesis, Geminal Cycloalkylation, and
Lithium-Titanium Exchange**
By Jurgen VoNhardt. Hans-Joachim Gais,* and
Karl L. Lukas
Ab initio calculations for monomeric 1,l- and 1,3-dilithiopropene gave as an energy minimum an unusual doubly lithium-bridged structure, characterized by Streitwieser
et al."] as an "ion triplet of two lithium cations and a propenylidene dianion." 1,l-Dilithiopropenes containing a
sulfonyl group in the 1-position, which is capable of complexing lithium and which is preparatively useful in a variety of ways, are of great interest with regard to their structure in solution and in the crystal as well as their synthetic
potential. We describe here the synthesis of 1.1-dilithioallyl phenyl sulfone 4 , the first compound of this type, and
that of its isomer 3 as well as their geminal cycloalkylation
and lithium-titanium exchange.
The second lithiation of I-lithioallyl phenyl sulfone 2,
prepared from phenyl 2-propenyl sulfone 1, proceeds in a
remarkable fashion: in tetrahydrofuran (THF) at low temperatures, one equivalent of nBuLi metalates 2 in the position ortho to the sulfonyl groupI2I to give 3 in a kinetically
controlled reaction with high selectivity; metalation in the
I-position to give 4 occurs as well. The selectivity decreases with increasing temperature. Upon warming 3 to
50°C in THF, complete transmetalation to the thermodynamically more stable 1,l-dilithio species 4 takes place.
The metalation of 2 and the transmetalation of 3 can be
followed by 'H-NMR spectroscopy.
In T H F at - 50"C, 3 reacts with excess benzaldehyde to
give the 1,o- and 3,o-(E)-diadducts 5 (74%) and 6 (4%), respectively, while 4 affords the 1,3-(E)-diadduct 7 in nearly
the same yield (77%).
When [1-D,]-2 is lithiated, a mixture of [1-Dl]-3/4 is obtained, which upon warming to 50°C is completely converted into [o-Dl]-4/4 within 2 h ; after protonation with
HCI/H,O/THF, [o-D,]-l/l is obtained and its composition determined by 'H-NMR spectroscopy. At -35°C in
THF, 2 is lithiated with 90% selectivity and [1-Dl]-2 with
97% selectivity by nBuLi.I3]
4 is only sparingly soluble in T H F and remarkably stable. After 4 h at 50"C, deuteration with DCI/D,O/THF
( O T ) still afforded 82% [1,1-D2]-1 (degree of deuteration
298%). Interestingly, 4 reacts with CF,CO,D in T H F
( O T ) , undergoing both 1,l- and 1,3-dideuteration, to give
a 1 : 1 mixture of [l,l-D2]-phenyl 2-propenyl sulfone ([l,lD2]-1) and [1,3-D2]-phenyl 1-propenyl sulfone ( E : Z =17 : 1)
(degree of deuteration 295% in each case).
The dialkylation of 4 with methyl iodide (THF, - 50°C)
proceeds regioselectively ( 2 98%) to give the 1, I-dimethylally1 sulfone 8 (80%). The same is observed for the cycloalkylation of 4 with 1,o-dibromoalkanes (THF, 0°C) to give
the carbocyclic compounds 9a (449/0), 9b (SOYO),and 9c
(89%). By geminal cycloalkylation of 4 with the ditosylates
10 and llI4](THF, 25'C), it is possible to synthesize the
new bicyclic compounds 12 (77%, ds=70%) and 13 (82V0,
ds = go%), respectively, in high yield and with high diastereoselectivity (ds); these compounds are geminally disubstituted with a vinyl and a phenylsulfonyl group. 13 could
eventually be converted by "y-substitution" with lithium
dialkylcuprates['' into the 6a-carbapro~tacyclin~~~
14 (Scheme 2).
Scheme 2
Surprisingly, nearly the same results are obtained for the
methylation and the cycloalkylation of the 1,o-dilithio
compound 3. The initial alkylation of 3 in the 1-position
to give the o-lithiophenyl sulfone 15 is followed by complete transmetalation to the 1-lithioallyl sulfone 16
(Scheme 3), which affords 8, 9, 12, or 13 upon a second
alkylation or upon c y ~ l o a l k y l a t i o n . ~ ~ ~
Scheme I . R=PhCH(OH).
Scheme 3 .
Gais, Dipl.-Ing. J. Vollhardt, Dr. K. L. Lukas ['I
Institut fur Organische Chemie und Biochemie der
Technischen Hochschule
Petersenstrase 22, D-6100 Darmstadt (FRG)
Present address:
Chemische Werke Huls AG, Abtlg. Biotechnologie, D-4690 Heme (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
[*] Priv.-Doz. Dr. H:J.
0 VCH Verlagsgesellschaft mbH. 0-6940 Weinheim, 1985
2 reacts regioselectively with benzaldehyde and cyclopentanone (THF, - 7 0 ° C ) to give the 1-adducts 17a (85%,
1 :1 diastereomeric mixture) and 17b (92%), respectively.
Very similar results are obtained when 2 is first converted
into the ,allyltitaniurn species with one equivalent of
(iPrO)2TiC12(THF, -SOT), which is then allowed to react
with the carbonyl compound (THF, 0°C): 82% 17a and
0570-0833/85/0707-0610 $ 02.50/0
Angew. Chem. Inf. Ed. Engl. 24 (1985) No. 7
91% 17b. The titanation1’I of the 1,o-dilithio compound 3
with one equivalent of (iPrO2)TiCI2(THF, -40°C; color
change from orange to red) affords a reactive titanium species, which gives [o-D,]-17b (degree of deuteration 85%) in
76% yield upon reaction with cyclopentanone (THF, 0°C)
followed by DCl/D20 work-up.
X = OiPr
Received: February 22, 1985;
revised: April 1 I, 1985 [ Z 1187 IE]
German version: Angew. Chem. 97 (1985) 607
a: R’ = P h , R2 = 11; b: R ’ - RZ = -(CHz)4-
The lithium-titanium exchange is achieved for the 1,ldilithio species 4 if it is allowed to react with (iPrO)2TiC12
at -70°C in T H F and the solution is then warmed to
- 10°C; a novel organotitanium compound is formed,
which until now has only been prepared as a deep red solution. It is deuterated to [l,l-D2]-l (78%, degree of deuteration 2 9 8 % ) similarly to 4 with DC1/D20; however, in
contrast to 4, it does not react with methyl iodide under
the same conditions. With aldehydes (THF, -50°C) and
ketones (THF, -50 to OOC), on the other hand, both the
dienes 18 and the 3-adducts 19 are obtained, which, upon
trapping with DCI/D,O, are shown to contain deuterium
in the 1-position (e.g., [l-D,]-19a, degree of deuteration
90% (Scheme 4).
4/ ( i P r O )2TiCl 2
R 2 18
a: P h
b: t B u
e: P h
+ 1%2-SOzPh
1% 1
5 (El
5 (E)
77 ( E )
68 ( E )
73 ( E )
f : -(CH2)4-
38 ( E : Z = 3:2)
48 ( E : Z = 9:l)
41 ( E : Z = 9:l)
31 ( E )
CAS Registry numbers:
1, 16212-05-8; [I,l-D2]-1,97072-58-7; 2,97072-31-6: [l-Dl]-2,97072-59-8; 3,
97072-32-7: [l-D,]-3, 97072-60-1; 4 , 97072-33-8; [o-D,]-4, 97072-61-2; 5 ,
97072-34-9; 6 , 97072-35-0; 7, 97102-06-2: [o-Dl]-7, 97072-62-3; 8 , 72863-208; 9a, 97072-36-1: 9b, 97072-43-0; 9c, 97072-44-1: 10, 32970-96-0; 11,
97072-37-2: 12, 97072-38-3; 13, 97072-39-4; 14, 97072-40-7: 17a. 97072-418 ; 17b, 97072-42-9, [o-D]-17b, 97072-65-6; 18a, 97072-45-2; 18b. 97072-47-4:
(E)-18d, 97072-50-9; (z)-lSd, 97072-51-0; (E)-18e, 97072-54-3; (Z)-lSe,
97072-55-4; 18f, 97072-57-6: (E)-19a, 97072-46-3; (z)-19a, 97072-66-7; [ I D]. 19a, 97072-67-8: 19b, 97072-48-5: 19e, 97072-49-6; (E)-19d, 97072-52- I;
(Z)-19d, 97072-53-2; 19e, 97072-56-5; (i-Pro)>TiCI>,762-99-2; Br(CHZ)>Br,
106-93-4; Br(CH2),Br, 109-64-8: Br(CH,),Br, 110-52-1: PhCHO, 100-52-7; IBuCHO, 630-19-3: CI,CCHO, 75-87-6; MeCHO, 75-07-0; PhCOMe, 98-86-2:
(E)-[1,3-DzJ-phenyl 1-propenyl sulfone, 97072-63-4; (Z)-[1,3-D2]-phenyl Ipropenyl sulfone, 97072-64-5: cyclopentanone, 120-92-3.
[I] D. Kost, J. Klein, A. Streitwieser, Jr., G. W. Schriver, Doc. Natl. Acad.
Sci. US4 79 (1982) 3922; cf. P. von R. Schleyer, A. J. Kos, J. Chem. Soc.
Chem. Commun. 1982. 449.
[2] H. W. Gschwend, H. R. Rodriguez, Org. React. 26 (1979) I.
131 The lower o-selectivity of the lithiation of 2 in comparison with that of
[1-D,j-2 could be caused by the isotope effect or, alternatively, it may be
only apparent due to transmetalation during the trapping of 3 with benzaldehyde (see Scheme 3).
(41 Synthesis of 11 from cis-4-cyclohexene-l,2-dimethanol:
H:J. Gais, Hahilitationsschrift, Technische Hochschule Darmstadt 198 I.
151 Cf. Y. Masaki, K. Sakuma, K. Kaji, J. Chem. Soc. Chem. Commun. IY80.
[6] P. A. Aristoff, J. Org. Chem. 46 (1981) 1954, and references cited therein.
171 The deuteration of 3 is also accompanied by transmetalation: [o-Do,/lD, ,]-I is obtained with CF3C02Dand [o-Do4/l-D,.6J-lwith DCI/D20.
[8] M. T. Reetz, Top. Curr. Chem. 106 (1982) I; B. Weidmann, D. Seebach,
Angew. Chem. 95 (1983) 12: Angew. Chem. Inr. Ed. Engl. 22 (1983) 31.
[9] We thank a referee for this suggestion.
Scheme 4
The fact that sterically hindered aldehydes react with 4 /
(iPrO)2TiC12to form selectively the 3-(E)-adducts 19 could
be synthetically useful since 2 and 2/(iPr0),TiCl2 as well
as 3/(iPr0)2TiC12 give selectively the 1-adduct 17. The
reaction of 4/(iP1-0)~TiCl~
with cyclopentanone to give the
carbonyl olefination product 18f in good yield is also
The following finding deserves attention in connection
with the structure of the titanium species formed by metal
exchange on 4 : when one equivalent of lithium diisopropylamide is added at -50°C to the allyltitanium species
formed from 2 (one equivalent (iPr0)2TiC12, THF,
- 50°C) and the mixture warmed to - l O T , a deep red
solution (color change from orange to red) is obtained,
from which, after addition of benzaldehyde, 34% of the 1adduct 17a, 4% of the diene 18a, and 47% of the 3-adduct
19a ( E :Z = 3 :2) are obtained. The results of the reaction
of 4/(iPrO)2TiC12 with carbonyl compounds can be explained by the presence of a titanium species that contains
the partial structures 20A and 20B, which are interconvertible;l9I another possibility is the alkylidenetitanium complex 21.
Angew Chem. Int. Ed. Engl. 24 (1985) No. 7
Reaction of Homobenzvalene with Tetracyanoethylene;
Formation of a Tetracyanodihydrobarbaralane
Derivative and a Tetracyanocyclopropane
By Manfred Christl,* Reinhard Lang. Clemens Herzog,
Roland Stangl, Karl Peters, Eva-Maria Peters, and
Hans Georg von Schnering
Dedicated to Professor Rorf Huisgen on the occasion of his
65th birthday
The reactions of tetracyanoethylene (TCNE) and 5,6dichloro-2,3-dicyano-p-benzoquinone
with benzvalene recently reported by us constitute the first documented examples of the long sought after one-step 1,4-cycloaddition
of an alkene to a vinylcyclopropane.””I As a
[*I Prof. Dr. M. Christl, Dr. R. Lang, Dipl.-Chem. C. Herzog,
Dr. R. Stangl
Institut fur Organische Chemie der Universitat
Am Hubland, D-8700 Wunburg (FRG)
Dr. K. Peters, E.-M. Peters, Prof. Dr. H. G. von Schnering
Max-Planck-Institut fur Festkorperforschung
Heisenbergstrasse 1, D-7000 Stuttgart 80 (FRG)
This work was supported by the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie.
0 VCH Verlagsgesellschafi mbH, 0-6940 Weinheim. 1985
0570-0833/85/0707-0611 $ 02.50/0
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cycloalkylation, exchanger, titanium, synthesis, dilithioallyl, geminal, phenyl, sulfone, lithium
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