Carbonyl allenylations and propargylations by 3-chloro-1-propyne or 2-propynyl mesylates with tin(IV) chloride and tetrabutylammonium iodide

Article abstract of DOI:10.1055/s-2003-41012

By the use of tin(IV) chloride and tetrabutylammonium iodide in dichloromethane, 3-chloro-1-propyne or 2-propynyl mesylate can be applied to allenylation and propargylation of aldehydes (carbonyl allenylation and propargylation) to produce a mixture of 1-

Full text of DOI:10.1055/s-2003-41012

LETTER
1713
Carbonyl Allenylations and Propargylations by 3-Chloro-1-propyne or 2-
Propynyl Mesylates with Tin(IV) Chloride and Tetrabutylammonium Iodide
C
arbonyl Allenyla
o
tions and Pro
s
pargylatio
h
ns iro Masuyama,* Akiko Watabe, Yasuhiko Kurusu
Department of Chemistry, Faculty of Science and Technology, Sophia University, 7-1 Kioicho, Chiyoda-ku, Tokyo 102-8554, Japan
Fax +81(3)32383361; E-mail: y-masuya@sophia.ac.jp
Received 19 June 2003
Abstract: By the use of tin(IV) chloride and tetrabutylammonium
iodide in dichloromethane, 3-chloro-1-propyne or 2-propynyl
mesylate can be applied to allenylation and propargylation of alde-
hydes (carbonyl allenylation and propargylation) to produce a mix-
ture of 1-substituted 2,3-butadien-1-ols and 1-substituted 3-butyn-
1-ols. 1-Substituted 2-propynyl mesylates selectively cause carbon-
yl propargylation, while 3-substituted 2-propynyl mesylates cause
carbonyl allenylation.
Key words: nucleophilic additions, allenylations, propargylations,
organometallic reagents, tin(IV) chloride
Alkynes and allenes are attractive synthetic tools for high
Scheme 1
reactivities to metal complexes or reagents.1 Thus, the
preparation of alkynes and allenes becomes an important
The allenylation and propargylation of benzaldehyde by
3-chloro-1-propyne (1a) with tin(IV) chloride and TBAI
were investigated under various conditions. Some repre-
theme. Barbier-type carbonyl allenylation or propargyla-
tion with propargylic halides is one of the most conve-
nient methods for introduction of allenyl or propargyl
sentative results are summarized in Table 1 (entries 1–3).
function.2 However, it is not so easy to control the selec-
The optimum method proved to be the same as that of the
tivity between the allenylation and the propargylation
carbonyl allylations by 2-propenyl mesylate with tin(IV)
with propargylic halides. We have established that either
chloride and TBAI (entry 2).5,7 The reaction at 0 ºC for 46
hours lowered the yield (46%) of products 2 and 3 without
Barbier-type carbonyl allenylations or propargylations by
3-halo-1-propynes or 2-propynyl mesylates with tin(II)
enhancing the selectivity of either allenylation or prop-
halides and tetrabutylammonium halides can be con-
argylation. No reaction occurred at temperatures below
trolled by reaction conditions3 and by varying the bulki-
–20 °C. Stirring the solution of 3-chloro-1-propyne (2.0
ness of substituents.4 The allenylations or propargylations
mmol), tin(IV) chloride (2.0 mmol), and TBAI (6.0
by 3- or 1-substituted 2-propynyl mesylates need high-
mmol) in CH2Cl2 at room temperature for 24 hours, add-
boiling polar solvents such as 1,3-dimethylimidazolidin-
ing benzaldehyde (1.0 mmol) and further stirring the solu-
2-one and DMF to dissolve tin(II) iodide, though the sol-
tion for 24 hours afforded a slightly lower yield than that
vents make workup troublesome.4 We have recently
of entry 2 (76%, 2:3 = 65:35). Carbonyl allenylations and
propargylations using 1a and 2-propynyl mesylates 1b–f
were carried out with various aldehydes under the same
found that tin(II) chloride, in situ prepared by the reduc-
tion of tin(IV) chloride with tetrabutylammonium iodide
(TBAI), can be applied to carbonyl allylations by 3-halo-
conditions as those of entry 2 (entries 4–29 in Table 1).
1-propenes or 2-propenyl mesylate in low-boiling nonpo-
The selectivity between allenylation and propargylation
lar dichloromethane.5 We here report on the carbonyl al-
can be controlled by the bulkiness of 1- or 3-substituents
lenylations and propargylations by 3-chloro-1-propyne
of 2-propynyl mesylates 1c–f; 3-substituted 2-propynyl
mesylates 1c and 1d preferentially cause the allenylation
of aldehydes, while 1-substituted 2-propynyl mesylates 1e
and 1f dominantly cause the propargylation of aldehydes.
and 2-propynyl mesylate via the in situ preparation of
tin(II) species from tin(IV) chloride and TBAI in dichlo-
romethane. We describe some applications to steric fac-
tor-mediated selective carbonyl allenylations or
This carbonyl allenylation and propargylation are out-
propargylations by 3- or 1-substituted 2-propynyl mesy-
lined in Scheme 2, by reference to the carbonyl allylation
lates respectively (Scheme 1).6
by 3-halo-1-propenes or 2-propenyl mesylate with SnCl4-
TBAI reagent.5 Iodide ion probably serves as a reducing
agent for preparing trichlorostannate(II) ion (–SnCl3) from
SnCl4 via the formation of pentacoordinate stannate(IV)
ion (–SnCl4I), followed by the reductive elimination of io-
Synlett 2003, No. 11, Print: 02 09 2003. Web: 11 08 2003.
Art Id.1437-2096,E;2003,0,11,1713,1715,ftx,en;U11803ST.pdf.
dine monochloride (I-Cl). The trichlorostannate(II) ion
DOI: 10.1055/s-2003-41012
may cause nucleophilic substitution to propargyl sub-
© Georg Thieme Verlag Stuttgart · New York

1714
Y. Masuyama et al.
LETTER
Table 1 Carbonyl Allenylations and Propargylations with 1a
strates 1 preferentially to afford sterically unhindered pro-
pargyltrichlorotins (R1 = H) or allenyltrichlorotins
(R2 = H) that function as nucleophiles for carbonyl
allenylations or propargylations respectively. I-Cl may re-
act with two equimolar amounts of TBAI to produce
TBACl and tetrabutylammonium triiodide (TBAI3).
SnCl4–TBAI is a useful reagent for Barbier-type carbonyl
allenylation and propargylation without reducing alde-
hydes. This SnCl4–TBAI reagent is superior to SnI2–
TBAI reagent for the selective propargylation by 1-substi-
tuted 2-propynyl mesylates.4
Entry Sub-
strate
R3
Time 2+3; Yield 2/3 (3; syn/anti)c
(h)
24
24
48
23
23
(%)b
84
85
35
89
74
65
47
82
74
87
68
70
81
48
43
34
50
28
33
28
39
70
86
71
73
41
80
70
41
1d
2
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
1b
1b
1c
1c
1c
1c
1c
1d
1d
1d
1e
1e
1e
1e
1e
1f
Ph
60/40
Ph
60/40
3e
4
Ph
50/50
4-ClC6H4
4-MeC6H4
66/34
5
59/41
6
PhCH2CH2 45
62/38
7
C6H13
42
49
44
71
70
72
73
70
69
61/39
8
c-C6H11
Ph
70/30
9
54/46
10
4-ClC6H4
4-MeC6H4
C6H13
57/43
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
61/39
55/45
c-C6H11
Ph
65/35
70/30
4-ClC6H4
68/32
PhCH2CH2 72
76/24
C6H13
74
72
72
72
73
72
68
73/27
c-C6H11
Ph
73/27
91/9
4-ClC6H4
c-C6H11
Ph
>99/1
Scheme 2
93/7
Acknowledgment
2/98 (48/52)
0/100 (47/53)
2/98 (53/47)
2/98 (77/23)
0/100 (–)f
2/98 (46/54)
0/100 (48/52)
1/99 (85/15)
This work was supported by a Grant-in-Aid for Scientific Research
(C) (No.14540549) from the Japan Society for the Promotion of
Science (JSPS).
4-ClC6H4
PhCH=CH 69
C6H13
c-C6H11
Ph
73
74
71
70
72
References
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ried out in CH2Cl2 (2 mL) at r.t.
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Synlett 2003, No. 11, 1713–1715 © Thieme Stuttgart · New York

LETTER
1995, 25, 2938. (g) Houllemare, D.; Outurquin, F.;
Carbonyl Allenylations and Propargylations
1715
(7) A typical procedure is as follows: To the solution of 1a (2
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CH2Cl2 = 2:1) and washed successively with aq 10% HCl
solution (20 mL), aq NaHCO3 solution (20 mL), H2O (20
mL), and brine (20 mL). The extracts were dried over anhyd
MgSO4. After evaporation of solvent, purification by
column chromatography (silica gel, hexane:EtOAc = 10: 1)
and then HPLC (Japan Analytical Industry Co. Ltd., LC-
908; JAIGEL-2H; chloroform) afforded 124 mg (85%) of a
mixture (2:3 = 60:40) of 1-phenyl-2,3-butadien-1-ol (2; R1,
R2 = H, R3 = Ph) and 1-phenyl-3-butyn-1-ol (3; R1, R2 = H,
R3 = Ph) as a colorless oil. Rf = 0.33 (silica gel,
hexane:EtOAc = 3: 1). IR(neat): 3300, 3060, 3030, 2910,
2150, 1960, 1600, 1540, 1490, 1450, 1390, 1190, 1160,
1030, 910, 860, 760, 700, 640 cm–1. Compound 2: 1H NMR
(500 MHz, CDCl3): d = 2.11 (d, J = 3.5 Hz, 1 H), 4.90–4.98
(m, 2 H), 5.26–5.31 (br, 1 H), 5.45 (q, J = 6.5 Hz, 1 H), 7.27–
7.45 (m, 5 H). Compound 3: 1H NMR (500 MHz, CDCl3):
d = 2.08 (t, J = 2.5 Hz, 1 H), 2.35 (d, J = 3.0 Hz, 1 H), 2.63
(ddd, J = 11, 2.5, 1.0 Hz, 1 H), 2.67 (dd, J = 11, 2.5 Hz, 1
H), 4.86–4.91 (m, 1 H), 7.27–7.45 (m, 5 H).
Synlett 2003, No. 11, 1713–1715 © Thieme Stuttgart · New York