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Cleavage of Selenium Compounds by Butyllithium.

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[ 8 2 ] 7 01Ijii.\mu, J. B. F. N. Enyhwcs, and J . Sir-trirng, Rec. Trav. Chim.
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Chem. internat. Edit. IZ, 407 (1973).
[84] 0 If. 0 1 d m z i d and A. M . i’un Lrusen. Synth. Commun. 2, 281 (1972).
[85] For recognition of the relative configuration only one enantiomer
show8n.
[X6] Review: J . A . Frirnip, Chem. Rev. 71, 483 (1971).
is
[87] 1). Hoppe and U . Sddlkopf. Angew. Chem. 84. 435 (1972); Angew.
Chem. internat. Edit. / I , 432 (1972)
[88] M Su:uki, T. Iirusuki, K . Mur.\umo/o. and K . Okumurcr, Chem. Ind.
(London) IY73. 228.
[89] Y Harilrhrn. Gronau, personal communication.
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[91] U. SdGllkopf and D. Hoppr, Angew. Chem. 82, 483 (1970): Angew.
Chern. internat. Edit. Y, 459 (1970).
[92] A. I . Meyers and E W Cojlingron, J. Amer. Chem. SOC.92, 6676 (1970).
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1951 U: Jirng, Diplomarbeit, UniversitPt Gottingen 1974.
[96] 0 H. Oidmzicl and A . M. L U I T Luuscii, Tetrahedron Lett. lY74. 163.
[97] 0.H. OIdmzir1 and A . M. ran Lrii.srn, Tetrahedron Lett. 1974, 167.
[98] 1. H u g d o r f i and E. Etiing. Angew. Chem. 73, 26 (1961).
[99] R. Sc h r - o d ~Dissertation.
~,
Universitat Gottingen 1972.
[IOO] U . ScIiiillkopf and K. Schriidrr-, Angew. Chem. 83, 358 (1971): Angew.
Chem. internat. Edit. 10. 333 (1971).
[ 1011 E. Eilrrs. Dissertation. Universitit Gottingen 1974.
[102] D. Murqiiurdirig and 1. L‘gr, unpublished work, cited in ref. [4], p.
237.
[ 1031
(i. Schijllkopf.
R. Sc hriidPi-. D. H o p p ~ .and K. Jomd7. unpublished.
[lo41 Dehydration ofdiethyl forrnylaminomalonate also affords the 5-alkoxyoxazole; F Gerhart, unpublished work.
[IOS] It is surprising that the esters (125) d o not at least partially cyclize
under the alkaline reaction conditions since ethyl a-isocyanophenylacetate
on distillation: D. Hoppr. unpublished
gives mainly 5-ethoxy-4-phenqloxazole
uork.
[ 1061 P . 5iihmr. Dissertation, Universitit Gottingen 1974.
[ 1071 E. E i k r s . Diplomarbeit, Univei~sititGottingen 1970
[IOX]
A. M. ruii Ltwsrn and 0. If. Old~wizid,Tetrahedron Lett. 1972. 2373.
[I091 0. H. Oldrnzid and A . M . run Lru.srri, Teti-ahedron Lett 1972, 2777.
[ I 101 H . , M w n ~ ~ ~ i(1’
t i I.1orrun.
.
N. S ( k i i n , and G. Sropp, Liebigs Ann. Chern.
641, 111961).
[ I I I ] P.-H
Pur.wh. 1)issertation. Univei-sitit Gfittingen 1973
[ 1121 Reviews: C . Gilma~iand J . W Morron, Org. React. 8, 290 (1954):
R. C ./ones and H. Gilmun. ihid. 6. 358 (1951).
[ 1131 W Vuulhnrg, J. Srruririg, M. G. Woldring. and H . W”nherg, Synth.
Comrnun. 2.423 (1972).
[ 1141 D. Hoppr. unpublished.
[ I 151 G. Gokrl, P. Hoffmann. H . Ktrimann, If Klusacrk. G. Lurlke, D. Marqriording. and l. U g i in ref. [4], p. 205.
[I 161 Review. H. 0 Housr, [56], p. 595.
[ I171 U. Schiiilkopf and K Hanrke, Angew. Chem. X2. 932 (1970): Angew.
Chem. internat. Edit 9. 896 (1970).
[I IS] U . Shiillkopf and K . Hunrhe, Liebigs Ann. Chem. 1Y73, 1571.
[ 1191 U . Schijlikopfand P.-H. Poi-sdi.Angea. Chem. 84, 478 (1972). Angew.
Chem. internat Edit. 1 I , 429 (1972)
[IZO] L‘. S<hiA/Aop/ and P.-H. Porsch. Chem. Ber. 106, 3382 (1973).
[ 1211 K . Hunrkr, Diplomarbeit. Universitit Gottingen 1971.
[ I221 D.Stuffor-sf. Diplomarbeit. Universitat Gottingen 1971
[ 1231 A. M. run Liwsm, H. Sidivius, B. E. Hoogrnhooni. and D. w n Leusen.
Tetrahedron Lett 1972, 5337.
[ I241 J . E Bailhi iii. F. J. Ur-han, R. 0. G. Cooper, and F . L Jose, S. Amer.
Chem. SOC.Y5, 2401 (1973); G. A. Koppel and R. E. Korhler, rhid 95, 2403
(1973): R. A. Firrsronr and 5. G. Chrisrmsen, S. Org. Chem. 38, 1436 (1973):
W A . Slusurchik, H. E. Appirgurr, P. Funkc,. M! Kosrer. M. S. Puur, M.
Young. and ./. E. Doifmi, ihid 38, 943 (1973).
[I251 P. H 5mrlri. and J . P. Cluiron, J. C . S. Chem. Comm. 1974. 278.
[I261 W A. Spirzner and 7: Goodson, Tetrahedron Lett. 1973. 273.
[ I271 As recently reported. ( + J-(SJ-I-isocyano-2,2-diphenylcyclopropyllithium is configurationally stable below - 50°C. It follows that mesomeric
srabilization by the isocyano group plays no part: see’ H. M . Wuiborsky
and M. P. Prriusami, J. Amer. Chem. SOC.Y6. 371 I (1974).
Nores added in proof(November 21,1974):
[128] Very recently the first vinyl isocyanide (63) has been metalated:
E!Z-P-styryl isocyanide ( 6 3 ~ )was lithiated with n-butyllithium in tetrahydrofuran/n-pentane/diethylether ( 4 3 :1) at -110°C (trapped by methyl
iodide, trimethylchlorosilane, carbonyl compounds, and carbon dioxide);
U. Schollkopf and D.Stafforst, unpublished.
[129] 3- and 4-pyridylmethyl isocyanide were metalared with potassium
rerr-butoxide at -70°C and converted by carbonyl compounds into oxazolines of type (59), which underwent ring opening t o N-(1-pyridyl-1-alkeny1)formamides (3- or 4-pyridyl instead of CO,R in (71)) on warming to 0°C in
the presence of excess base. The reaction sequence with subsequent acid
hydro1ysisaffordsan“Einropf’synthesis of3- or4-pyridyl alkyl (orary1)ketones
of type (76) in yields of 60 to 80%; U. Srhoflkopf, E. Eitprs, and K . Hantke,
unpublished.
11301 See also M . Suzukt, M . Miyoshi, and K . Mnrsumoro, J. Org. Chem. 39.
1980 (1974).
[131] A synthesis of 3-amino-4-hydroxycumarins from ( 1 5 ) ria oxazoles is
reported by: K . Matsumoro, M. Suzuki, M Miyoshi, and K. Okumura, Synthesis
1974,500.
C 0 M M U N I CAT1 0 N S
Cleavage of Selenium Compounds by Butyllithiurn. A
New, Regiospecific, Ally1 Alcohol Synthon
By Willy Durnont, Pierre Bayet, and A . K r i r f [ * ]
In this paper, we describe the ready cleavage of selenonium
salts ( I ) [ I 1 and selenides ( 6 ) I 2 ]by n-butyllithium; subsequent
addition of a carbonyl compound to the reaction mixture
affords alcohols resulting mainly from the migration of one
of the substituents originally attached to the selenium.
Table 1. Alcohols ( 4 ) and ( 5 ) prepared according to Scheme I [3a]. ( l a ) .
R i = R 2 = R ’ = C H 3 , X = I : ( l h ) , R ’ = R 2 = C e H s , R”=CH3. X=BFI: ( / < I ,
R I = C hH5, R = R ” = C H z, X = CH 3SO 1.
’
r
54
75
45
16
~
28
12
54
L
4
,
/OII
F.
(4)
Scheme I
~~
..
40
40
32 [a1
70
49
+ selcnides
(5)
-
[*] Dr. W. Durnont, DipLChem. P. Bayet. and Prof. Dr. A. Krief
7
[**I
[d]
56
25
-
~
--
Departement de Chimie, Facultis Universitaires de Namur
61, rue de Bruxelles, B-5000 Namur (Belgium)
[**I O n leave from C N R S (France).
804
Angrw. Chem. internat. Edir.
Vol. 13 (1974)
No. 12
In some cases, butylated alcohols were also observed, especially
when trimethylselenonium iodide ( I a ) or dimethyl selenide
( h a ) were used (Tables 1 and 2).
While P-hydroxyselenides have already been obtained by the
ring opening of epoxides with selenophenolate161, cleavage
of unsymmetrically substituted epoxides can furnish two different P-hydroxyselenides. Such ambiguity is avoided by our
method. The exact position and nature of all of the substituents
(R'-R5) are strictly dependent on the choice of the two
carbonyl compounds.
Table 2. Alcohols ( X ) prepared according to Scheme 2 [3b].
.
~~
-.
~~~
~
..
-
-.
R'
(6)
(6h)
(6hJ
(6h)
(61')
( 6 0
(61.1
(6dJ
(61,)
(6t)
- - - -
~
Ri
RS
(8).
Yield
['XI
- ~ - ~ _ ~ _ ~ -
-.
. -~
(6u)
~
R2
~~
CH,
ChHs
C',H,
C~HI
ChHs
ChH?
C,HI
C,,Hr
C,,HsCHJ
C'hH,
CH.3
CHI
CHr
CH,
ChHs
CaHr
CoHs
CoHsCH2
CH,
CHz=CH-CHI
-
~
ChH,
CoHs
n-ChHI.,
ChHs
n-C6HI,
ChH'
C~HI
ChHs
n-C6H13
ChHs
32 [a]
93
68
27
85
74
72
75
30[b]
60
H
H
H
CHj
H
CH,
H
H
H
H
___
____
[a] I-Phenyl-I-pentanol was also isolated in 44"4 yield.
[b] 2-Octanol was also detected ( I
2 ";>).
SeC6H5
R~KZCH-C: /OH
R3/ /C,
R4 R5
-
R
'
,
,R3
,OH
c=c,
~I,o?
R'/
f 16)
Scheme 4
(17)
Table 4. B-Hydroxyselenides ( 16) und allyl alcohols ( 1 7 ) prepared according
to Scheme 4. Yields refer to purified products [7].
_
~
_
R'
~
R2
- - . ~.
~
R'
~
R'
(16)
RS
Yield
-_-__
~
Surprisingly, the use of &unsaturated carbonyl compounds
( 9 ) increased the proportion of butylation products (Table
3).
u
h
1'
d
c
H
H
H
H
H
H
H
H
H
CH;
CHI
CH.3
CHI
H
H
ChHi
H
-(CHdH
H
~-~
CH,
n-ChHI.,
n-fhHlr
n-C6HI
1/71
[z]
~. -. ~.
67
70
78
49
60
80
X0
93
78
74 [a1
[a] We presume that the stereochemistry of the carbon-carbon double bond
IS mainly trans (JH-H=15Hz).
I14CH=C\H /OH R4FH-C\H2
R4CH=C<J /OH
C
RI'
+
\1i5
HgC,/
C
\RS
C4H9
/c=o
R5
Table 3. Ally1 alcohols ( 1 0 1 and ( 1 1 ) and ketones ( 1 2 ) prepared according
to Scheme 3 [3a] f l u ) , R ' = R 2 = R 3 = C H 3 , X = l : ( I h ) , R 1 = R 2 = C 6 H 5 .
R"=CHj, X = B F 4 .
-
.~ .
~
_
OUJ
( J U J
(/hi
.
- -
~
R'
(1)
R'
-.
~
CH.3
CHI
C,H$
- .- .~ -.
~~
R'
~
..
~
... -
Cc,H5
H
ChHs
CbH5
ChHr
C,HS
.
.
..
(10)
- -
0 1 1
Yield
-
(12)
[%I
- -~ - .. -
26.5
20
47.5
7 [a1
31.5
42
17
40.5
-.
[a] Isolated as methyl ether.
Typically in ( I b ) , ( I c ) and (66), the phenyl group is
transferred preferentially to the methyl group.
To account for our results, we assume that addition of butyllithium to the selenium compound ( I ) or (6) leads to a
tetra- (2) or tri-substituted intermediate ( 7)L4]; subsequent
migration ofone of the substituents to the carbonyl compound
gives rise to the alcohol.
As a synthetic application of this Se-C cleavage, we describe
a new regiospecific synthesis of allyl alcohols ( 1 7 ) starting
formally from two carbonyl compounds [ ( I 3 1 and ( 3 ) ] . The
key step of this synthesis is the facile cleavage of selenoacetals
( 1 4 ) L s Jby n-butyllithium in T H F (-78°C) to give carbanions
(15) which add a variety of aldehydes and ketones ( 3 )
to form J3-hydroxyselenides (16) in good yields (Table 4).
Angew. Chrm. intrrnat. Edit.
/ Vof. 13 ( 1 9 7 4 ) / N o . 12
Finally, using Sharpless' procedure['] the hydroxyselenides
(16a)-(16e) are readily oxidized with hydrogen peroxide
(THF, 1h, 25°C) to give allyl alcohols (17) in high yield
(Table 4). We are currently investigating the scope and stereochemistry of these reactions, as well as the use of S e x
cleavage to generate carbanions which are difficult to obtain
by usual methods.
Received: July I . 1974; i n shortened form.
August 27. 1974 [ Z 90a I € ]
German version: Angew. Chem. X6, 857 (1974)
CAS Registry numbers: [ l a ) . 7362-34-7; [ l b ) . 52724-83-1 ; ( I c J ,
13118-29-1; (31, R4=C,Hs, R 5 = H . 100-52-7; (3),R4=C,H5.R5=CH,.
98-86-2; [3),R4=n-C,H,,, R S = H , 111-71-7; ( 3 ) . R 4 = R 5 = C 6 H ,
119-61-9; (31, R4,R5 =(CH2),CH(f-C,H,)(CH,),. 98-53-3; (31.
R4,R j --(CH2)5, 108-94-1 ; ( 6 a l , 593-79-3; (661, 4346-64-9: ( 6 c J ,
1132-39-4; 16d). 18255-05-5; 16e1, 5925-78-0; l 6 f ) . 14370-82-2;
(8).R' =C6H,CH2.R4=n-C6H13.RS = H, 19396-72-6: (9). R 4 = R S =C,H,,
94-41-7; 191, R4=C6HS,Rs=H,104-55-2; ( 1 3 ) , R ' = R 2 = H . R 3 = C H 3 .
61-64-1 ; ( I 3 ) , R ' = R Z = R 3 = H, 75-07-0; ( l 3 ) ,R ' = R 3 = H. R' =CHI,
123-38-6; [ l b a ) . 53188-71-9; ( l 6 b ) , 53188-72-0; ( 1 6 ~ )53188-73-1
.
:
(16d). 53188-74-2; ( 1 6 e ) . 53188-75-3; ( / ? a ) , 29290-99-1 ; [ l 7 h ) ,
52500-37-5; ( 1 7 ~ )3908-31-4.
.
(17d), 21964-44-3: 117e). 53188-77-5:
Butyllithium, 109-72-8 ; Bis(pheny1seleno)methane.20343-90-2 : (4).
R' =CH,, R"=C,H,, R S = H , 98-85-1 ; (41, R' = R S = C H , , R4=C,HS,
617-94-7; / 4 ) . R 1 = C H a , R 4 = n - C 6 H j 3 , R S = H , 123-96-6; [ 4 ) . R 1 = C H 3 .
R4 = R S =C6Hs,599-67-7; (41, R' =CH3,R4,RS=(CH,),CH(t-C~H.~UCH,),,
6353-54-4; [ 4 ) , R ' = R ' = C 6 H , RS=H,91-01-0; (4)%R'=C,H,,
R4=n-ChHl,,RS=H.614-54-0: ( 5 ) , R 4 = C 6 H , R S = H . 583-03-9;
(51, R4=n-C,H,,, R S = H , 37493-70.2; ( 5 ) . R 4 = R S = C , H 5 . 5384-63-4;
(51, R4,RS=(CH2)2CH(f-C4H9)(CH2)2,
53188-79-7; (10). R 1=CH3,
R 4 = R 5 = C 6 H s ,41231-78-1 : (10). R' =CH;, R4=C,H,, R s = H ,
17488-65-2; (10). R 1 = R 4 = RS=C,H,, 4663-36-9; (11). R 4 = R S=C,H,,
805
53188-81-1: ( / l J R4=C,H,,
,
R S = H . 20157-19-1; ( l 2 J . R 4 = R s = C , H s ,
1454-51-5
[ I ] Unstahilized selenonium ylides can be generated by reaction of suitable
bases with selcnonium salts: W D [ ! n m t . P. Bui.er, and A . Krii+ Angew.
C'hcni. 86. 30X ( 1974). Angew. Chem. internat. Edit. 13, 274 (1974).
[ 2 ] Simil;ir clcavage of some selenides has been described: a ) H . Giimuii
and R. L Behh. J. Amer. Chem Soc. 6/, 1110 (1939); b) H . Giiman and
F J . Webb,J Amer. Chem. Soc. 71, 4064 (1949): c) D. Seeharh and N .
Peieries, Angew. Chem. 81, 465 (1969); Angew. Chem. internat. Edit. 8, 450
(1969): d ) D. Seehaclt and N . Peieries. Chem. Ber. 105, 511 (1972) However.
no systematic stiidy was performed.
131 Reaction conditions: a ) T o a suspension of 6 m m o l of (I)in T H F
- 78°C. under N2)5.5 mmol of whutyllithium in hexane
(2.75mI). After IOmin. the carhonyl compound (5mmol in 5ml T H F ) was
introduced and the mixture mas allowed to react lor 2 h at -78°C and
I h at 20°C. h) To a solution of 6 m m o i of ( 6 ) in T H F 110ml) was added
(at 0 'C under N,) 5.5mmol of n-butyllithium in hexane (2.751~11).After 1 5 min
at 0°C and 30 rnin at 20°C. the carbonyl compound (S mmol in 5 mi T H F )
was introduced and the mixtiire was allowed to react for 2 h at 20°C.
i IOmli was added (at
[4] See a ) G. Wiiriq and H. Fritz. Liebigs Ann. Chem. 577. 41 (1962); h) D.
Helhiiiikel and G. Furhach. ihid. 7/5. 68 (1968).
[ 5 ] D. Sccho111 [2c, 2d] reported one example of this type: cleavage of
his(phenylse1eno)methanewith r~-hutyllithiiimto give phenylselenomethyllithium which was trapped by reaction with benrophenonc.
[6] K . B. Sharpir\\ and R. F . Luiici-. J. Amer. Chem. Soc.
YS. 2697 (197.1)
[7] Reaction conditions: T o a solution of sclenoketal ( 1 4 1 i5.2mmol) in
T H F ( I O m l ) was added a solution of n-butyllithium (5.2mmol) at -7X"C
tinder NL.After stirring for a further 1.5 h (not optimized), ( 3 ) ( 5 m m o l )
in T H F ( 5 m l ) was slowly introduced. The mixture was allowed to react
for 2 h at -78°C and 2 h ( 1 5 h with acetophcnone) at 25°C. hydrolyzed
and workcd up in the usual manner.
bony1 compounds to give olefins['ai and epoxides[2b1and for
the homologization of primary
However, a wide
range of variation of the transfer group seemed to be precluded[' b1 by the tendency of alkyl aryl sulfides containing higher
alkyl groups to undergo o-metalation on reaction with n-butyllithium. (Ring metalation is favored thermodynamically by
a factor of at least 50[31.)
We have now found CaH &/Li exchangeL4),which is comparable with Br/Li exchange, to offer a kinetically controlled
method for the preparation of secondary and tertiary phenylseleno- ( I ) and phenylthio-alkyllithium compounds (2). The
selenoacetals (3) obtained from aldehydes or ketones or by
alkylation of ( I ) , R=SeCsH5, R'= H[4b1are converted into
the selenium-substituted derivatives ( I ) within 15 min on
treatment with n- or tert-butyllithium in T H F at -80°C.
The products can be transformed by thiolation into the S,
Se acetals ( 4 ) which yield the sulfur-substituted derivatives
(2) on renewed transmetalation. Reaction of the organolithium compounds ( I ) or ( 2 ) with electrophiles furnishes the
products ( 5 ) and (6) respectively (Table 1).
As can be seen from Scheme 1, the phenylseleno- (7) and
phenylthio-alkyl alcohols ( 8 ) prepared with aldehydes and
ketones as electrophiles are actually formed by coupling of
the carbonyl C atoms of two aldehydes or ketones. The
selenium derivatives ( 7 ) can be oxidizedI5]to yield ally1 alcohols ( 9 ) or ( I O), e. g. ( 9 a ) from cyclohexanone and hexanal
(overall yield 50%)or ( 1 Ou) from cyclohexanone and acetone
(overall yield 65 'x>).Hence compounds of type ( 1 ) can be
regarded as masked vinyllithium compounds
Secondary and Tertiary Phenylthio- and Phenylselenoalkyllithium Compounds as Novel Reagents for the
Formation of C-C Bonds[***]
By Dieter Seehuch and Albert K . Beck[*]
Because of its pronounced nucleophilic character, phenylthiomethyllithium (21,R = R ' = H, which is readily accessible by
metalation of thioanisol['], has acquired considerable preparative significance as a CH2 synthon in methylenations of carR'
d
I
R\
/C=o
R'
.__.
[*I
~~
Prof. Dr. D. Seehach [**] and A K . Beck [**]
Gates and C r e h Laboratories of Chemistry
California Institute of Technology
Pasadena, Calif. 91 I09 (USA)
[**I Permanent
address. Institut f u r Organische Chemie der Universitat
63 Giessen, Ludwigstrasse 21 (Germany)
[***I This work was supported by
806
the Deutsche Forschungsgemeinschaft.
Scheme 1. Transformations possible with the organolithium compounds ( I
and ( 2 ) and ketones and aldehydes as electrophiles.
)
The olefins ( 1 1 ) and epoxides ( 1 2 ) should likewise be accessible from the selenium- (7)16' or sulfur-containing alcohols
(8)[2a,2b1 by known methods.
Angew. Chem. internat. Edit. 1 Vol. 13 (1974)
No. 12
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