Regioselective buta-1,3-dienylation of aldehydes via transmetallation of 2-tributylstannylbuta-1,3-diene

Article abstract of DOI:10.1055/s-1999-2787

Transmetallation of 2-tributylstannylbuta-1,3-diene with SnCl₄ followed by Lewis base promoted addition of the resulting 1-trichlorostannyl-2,3-butadiene to aldehydes in the presence of DMF allows their buta-1,3-dienylation to take place at the

Full text of DOI:10.1055/s-1999-2787

LETTER
1109
Regioselective Buta-1,3-dienylation of Aldehydes via Transmetallation of 2-
Tributylstannylbuta-1,3-diene
Meiming Luo, Yoshiharu Iwabuchi, Susumi Hatakeyama*
Faculty of Pharmaceutical Sciences, Nagasaki University, Nagasaki 852-8521, Japan
Fax +81-95-848-4286; E-mail: susumi@net.nagasaki-u.ac.jp
Received 14 April 1999
To assay the possibility of the above-mentioned approach
Abstract: Transmetallation of 2-tributylstannylbuta-1,3-diene with
we first surveyed various Lewis acids (SnCl4,6 BCl3,
SnCl4 followed by Lewis base promoted addition of the resulting 1-
TiCl4,6 SiCl4, InCl3,8 CoCl2 ) in the reaction of 3 with hy-
9
trichlorostannyl-2,3-butadiene to aldehydes in the presence of DMF
drocinnamaldehyde. Thus, 2-tributylstannylbuta-1,3-di-
ene 3 was treated with Lewis acid in CH2Cl2 and after
disappearance of 3 on TLC, hydrocinnamaldehyde was
added to the reaction mixture. As shown in Table 1,10 only
SnCl4 and BCl3 turned out to promote the desired reaction
to give dienol 1 (R = CH2CH2Ph) although the yields were
moderate (entries 2 and 4). 2-Tributylstannylbuta-1,3-di-
ene 3 itself did not react with hydrocinnamaldehyde even
under refluxing conditions when no Lewis acid was used
(entry 1). It should be stressed that addition of DMF,
HMPA, or isoquinoline N-oxide dramatically improved
the yield of this reaction, in particular, when SnCl4 was
used for the transmetallation (entries 5-7 and 9).
allows their buta-1,3-dienylation to take place at the C2 position
with complete regioselectivity in high yields.
Key words: buta-1,3-dienes, tin compounds, transmetallations,
buta-1,3-dienylations, Lewis base promoted reaction
Dienols of general structure 1 are valuable precursors for
the syntheses of a variety of natural products.1,2 Buta-1,3-
dienylation of aldehydes utilizing 2-metallated buta-1,3-
dienes 2 derived from 2-chlorobuta-1,3-diene (chloro-
prene), an industrial material, is obviously the simplest
approach for the synthesis of 1 although several other
methods have already been developed.3 However, exist-
ing methods4 using 2 (M = MgCl or Li) following this ap-
proach have the serious disadvantage of poor
regioselectivity or low chemical yield. We now report a
facile and efficient buta-1,3-dienylation of aldehydes giv-
ing 1 with complete regioselectivity by use of 2-tributyl-
stannylbuta-1,3-diene 3, readily available from
chloroprene.3e,5
OH
M
R
1
2
Allylstannanes are known to react with Lewis acids
(MXn) to generate the corresponding allylmetal com-
pounds through a transmetallation process normally with
migration of the olefinic double bond.6 We envisaged that
such transmetallation of 2-tributylstannylbuta-1,3-diene 3
would produce buta-2,3-dienylmetal 4, which is expected
to react with aldehydes in 1,3-rearrangement fashion7 to
give dienols 1.
SnBu3
MXn-1
MXn
RCHO
•
1
– Bu3SnX
3
4
Scheme 1
Synlett 1999, No. 07, 1109–1111 ISSN 0936-5214 © Thieme Stuttgart · New York

1110
M. Luo et al.
LETTER
Table 2 summarizes SnCl4 promoted addition of 3 to var- ordination and only coordinated 5 participates in the reac-
ious aldehydes. It is evident that this reaction proceeds tion with an aldehyde possibly via six-centered cyclic
with complete regioselectivity and has broad applicability transition structure 7 even if both 5 and 6 exist as coordi-
for the preparation of 1. Entry 6 clearly indicates the nated complexes. This reaction, therefore, can be regarded
chemoselectivity of this reaction and an acetal group is in- as Lewis base promoted reaction of 1-trichlorostannyl-
tact under the reaction conditions, showing its advantage buta-2,3-dinene with an aldehyde, similar to the recent-
in comparison with other buta-1,3-dienylations.3 The di- ly discovered reactions of allylhalosilanes14 and allyl-
astereoselectivity of this reaction can be also evaluated by halostannanes.6c,15
the examples listed in entries 7-9 and high anti-selectivity
(80% de) was observed in the case of 2,3-O-isoprop-
ylidene-D-glyceraldehyde.
SnBu3
SnCl3
SnCl4
SnCl3
•
3
5
6
DMF
R
O
SnCl3
•
7
Scheme 2
In conclusion, we have developed a simple buta-1,3-die-
nylation of aldehydes giving 1 using readily available 2-
tributylstannylbuta-1,3-diene 3 as the diene source. The
present work exhibits the first example of Lewis base pro-
moted reaction of 1-trichlorostannylbuta-2,3-dinene 5
prepared in situ by transmetallation of 2-tributylstannyl-
buta-1,3-diene 3 with SnCl4. The development of an
asymmetric version of this reaction using a chiral Lewis
base ligand is the focus of current investigations.
Acknowledgment
This work was supported by the Japan Society for the Promotion of
Science (postdoctoral fellowship for M.L.). We gratefully acknow-
ledge Tosoh Corporation (Nanyo Reserch Laboratory, Japan) for
providing chloroprene.
References and Notes
In order to further understand this reaction, the following
NMR experiments were undertaken. Thus, 3 was treated
with 1 equivalent of SnCl4 at –60 °C in CDCl3 and after
completion of the transmetallation, 3 equivalent of DMF
were added and then the mixture was allowed to warm
to room temperature. After 30 min at room temperature,
1-trichlorostannylbuta-2,3-diene 511 and 2-trichlorostan-
nylbuta-1,3-diene 612 were observed in a ratio of ca. 1:1
each as complex with DMF and this ratio changed only
slightly even after 6 h.13 Interestingly, when hydrocinna-
maldehyde was added to this mixture, dienol 1
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1
(R = CH2CH2Ph) was produced in ca. 40% yield by H
NMR-measurement. On the other hand, in a control ex-
periment without DMF, 5 isomerized to 6 completely
within 6 h and addition of hydrocinnamaldehyde and
DMF to this mixture did not cause production of dienol 1
(R = CH2CH2Ph) at all. These results suggest that addition
of DMF retards the isomerization rate from 5 to 6 by co-
Synlett 1999, No. 07, 1109–1111 ISSN 0936-5214 © Thieme Stuttgart · New York

LETTER
Regioselective Buta-1,3-dienylation of Aldehydes via Transmetallation
1111
(5) a) Wada, E.; Kanemasa, S.; Fujiwara, I.; Tsuge, O. Bull.
Chem. Soc. Jpn. 1985, 58, 1942. b) Bates, G. S.; Fryzuk, M.
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1508. b) Marshall, J. A. Chem. Rev. 1996, 96, 31. c) Thomas,
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not given. When DMF was added, two methylene peaks
shifted to 4.84 and 2.65, respectively but the corresponding
methine peak could not be clearly identified.
(12) 1H NMR (CDCl3, 300 MHz) d 6.75 (dd, J = 16.8, 10.2 Hz,
1H), 6.23 (s, 1H), 5.90 (s, 1H), 5.56 (d, J = 16.8 Hz, 1H), 5.56
(d, J = 10.2 Hz, 1H)); 2J(117 and 119Sn-1H) are not given. When
DMF was added, these peaks shifted to 6.72, 6.15, 5.89, 5.43,
and 5.32, respectively.
(7) Buta-2,3-dienylsilanes, stannanes, and boronates are known to
react with aldehydes regioselectively in 1,3-rearrangement
fashion (see ref. 3).
(13) DMF-complex of 5 isomerized to DMF-complex of 6 almost
completely 30 h later.
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b) Denmark, S. E.; Coe, D. M.; Pratt, N. E.; Griedel, B. D.
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(9) Iqbal, J.; Joseph, S. P. Tetrahedron Lett. 1989, 30, 2421.
(10) Representative procedure (entry 5 in Table 1): To a stirred
solution of 3 (342 mg, 1.0 mmol) in CH2Cl2 (4 ml) at –78 °C
under argon was added SnCl4 (117 ml, 1.0 mmol). After
stirring at –78 °C for 45 min, DMF (232 ml, 3.0 mmol) was
added and the mixture was stirred at –78 °C for 10 min.
Hydrocinnamaldehyde (67 mg, 0.5 mmol) was added and the
mixture was allowed to warm to room temperature. After 12
h, the reaction mixture was basified with 5% NaOH (5 ml) and
extracted with Et2O. The extract was washed with water, dried
over MgSO4, and concentrated in vacuo. Purification by
column chromatography [SiO2 (10 g) pretreated with Et3N (1
g), n-hexane : AcOEt = 8:1] afforded 1 (R = Ph(CH2)2) (82.5
mg, 88%).
(15) Kobayashi, S.; Nishio, K. Tetrahedron Lett. 1995, 36, 6729.
Article Identifier:
1437-2096,E;1999,0,07,1109,1111,ftx,en;Y08899ST.pdf
(11) 1H NMR (CDCl3, 300 MHz) d 5.37 (m), 5.01 (dt, J = 6.6, 2.5
Hz, 2H), 3.03 (dt, J = 8.2, 2.5 Hz, 2H); 2J(117 and 119Sn-1H) are
Synlett 1999, No. 07, 1109–1111 ISSN 0936-5214 © Thieme Stuttgart · New York