Allylation of Carbonyl Compounds Bearing a Hydroxyl Group by Tetraallyltin: Highly Stereoselective Allylation in a Chelation-Controlled Manner

Full text of DOI:10.1021/jo9805697

J . Org. Chem. 1998, 63, 6401-6404
6401
Ta ble 1. Allyla tion of O-Su bstitu ted Ben za ld eh yd es 2
Allyla tion of Ca r bon yl Com p ou n d s Bea r in g
a Hyd r oxyl Gr ou p by Tetr a a llyltin : High ly
Ster eoselective Allyla tion in a
by Tetr a a llyltin 1a
Ch ela tion -Con tr olled Ma n n er
Makoto Yasuda, Tatsuya Fujibayashi, and Akio Baba*
Department of Applied Chemistry, Faculty of Engineering,
Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871,
J apan
Received March 30, 1998
In tr od u ction
Allylation of carbonyl compounds is an important
method for forming carbon-carbon bonds. Many re-
agents have been developed for such allylations over the
past few decades.1 Allyltrialkyl or triaryltin compounds
are widely used for stereoselective allylations.2 However,
they are limited from the viewpoint of a practical
synthetic method: (i) They are inert to carbonyls such
as simple aldehydes or ketones without activators. Proper
activation is essential and has been widely studied; for
example, the use of Lewis acids1,2 for the activation of
electrophiles. (ii) Three substituents other than the
allylic one are disposed on the tin atom. They are
considered to be dummy substituents and are not trans-
ferable. To overcome these problems, tetraallyl-substi-
tuted stannane could be used as a reagent. Young
previously reported an effective allylation system using
a quarter equivalent of tetraallyltin to carbonyls in
methanol (eq 1).3-6 In this paper, we report the reaction
of tetraallyltin with carbonyls bearing a hydroxyl group
(eq 2). The intramolecular hydroxyl groups in this
system promote kinetic-controlled allylation via a che-
lation-model transition state with high stereoselectivity
as well as high efficiency.
Resu lts a n d Discu ssion s
Reaction s of Tetr aallyltin with Hydr oxy- or Meth -
oxyben za ld eh yd e. Table 1 shows the results of allyla-
tion of the substituted benzaldehydes 2 with tetraallyltin
(1). Salicylaldehyde (2b) was effectively allylated without
any promoters in toluene, while the allylation of benzal-
dehyde (2a ) did not proceed at all under the same
conditions (entries 1 and 2). 3-Hydroxybenzaldehyde (2c)
also gave the homoallylic alcohol 3c in high yield (entry
3). The phenolic hydroxyl groups in aldehydes were
indispensable for these allylations7 because the corre-
sponding methoxy-substituted aldehydes 2d and 2e were
inert in this system (entries 4 and 5). We tried the
allylation of a mixture of 2b and 2d (tetraallyltin:2b:2d
) 0.25:1:1, 25 °C, 1 h). This reaction gave the products
3b and 3d in yields of 51 and 46%, respectively. This
result suggests that the activation of carbonyl by an
acidic hydroxyl group (phenolic OH) is not significant for
this allylation, since even the aldehyde 2b, which has
an intramolecular hydrogen bond, had the same reactiv-
ity as 2d . Therefore, we can conclude that the acidic
(1) (a) Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207-2293.
(b) Yamamoto, Y. Acc. Chem. Res. 1987, 20, 243-249.
(2) Nishigaichi, Y.; Takuwa, A.; Naruta, Y.; Maruyama K. Tetrahe-
dron 1993, 49, 7395-7426.
(3) Cokley, T. M.; Harvey, P. J .; Marshall, R. L.; McCluskey, A.;
Young, D. J . J . Org. Chem. 1997, 62, 1961-1964.
(4) Cokley, T. M.; Marshall, R. L.; McCluskey, A.; Young, D. J .
Tetrahedron Lett. 1996, 37, 1905-1908.
(5) We independently investigated this type of acceleration system
in alcohols. (a) Yasuda, M.; Fujibayashi, T.; Shibata, I.; Baba, A. 70th
Annual Meeting of the Chemical Society of J apan, Abstr. No. 1J 226
(March 1996). (b) Yasuda, M.; Fujibayashi, T.; Baba, A. 43rd Sympo-
sium on Organometallic Chemistry, J apan, 1996, Abstr. B207.
(6) Effective allylations with one-fourth the amount of tetraallyltin
in the presence of Bro¨nsted or Lewis acids under aqueous conditions
have been reported. (a) Yanagisawa, A.; Inoue, H.; Morodome, M.;
Yamamoto, H. J . Am. Chem. Soc. 1993, 115, 10356-10357. (b)
Hachiya, I.; Kobayashi, S. J . Org. Chem. 1993, 58, 6958-6960. (c)
Kobayashi, S.; Nagayama, S. J . Org. Chem. 1996, 61, 2256-2257.
(7) We recently reported that phenol was effective for the allylation
of simple ketones by tetraallyltin. Yasuda, M.; Kitahara, N.; Fujiba-
yashi, T.; Baba, A. Chem. Lett. 1998, 743-744. This system requires
the premixing of phenol and tetraallyltin under heating to form a
reactive aryloxyallyltin species with comsumption of some allyl groups
of tetraallyltin. On the other hand, the reaction in this paper did not
proceed via the activation manner because nearly quantitative forma-
tion of the product was obtained with one-fourth the amont of
tetraallyltin.
S0022-3263(98)00569-6 CCC: $15.00 © 1998 American Chemical Society
Published on Web 08/08/1998

6402 J . Org. Chem., Vol. 63, No. 18, 1998
Notes
Sch em e 1
gave the allylated product 13a selectively in either
toluene or MeOH. In this case too, MeOH induced high
efficiency (>99% yield), and did not impede the formation
of a chelation intermediate, to give complete diastereo-
selectivity. On the other hand, the reactions of methoxy-
ketone 12b showed low efficiency and selectivity in both
solvents. X-ray studies revealed the relative configura-
tions of the products 13a and 13b, which are formed in
a chelation-controlled manner as shown in Scheme 4.
Kira and Sakurai reported an effective system for the
chelation-controlled allylation of 12a using trifluorosilane
with Et3N.12 The base acts as a deprotonating reagent
to form a covalent bond between the silicon center and
the oxygen. In our present system, chelation control was
attained via coordinative interaction between the tin
center and the hydroxyl oxygen, where no deprotonation
from the hydroxyl group was required.
Con clu sion . In summary, the intramolecular hy-
droxyl group in carbonyl compounds acts as the reaction
promoter and selectivity controller in allylation with
tetraallyltin. The allylation of hydroxyl-substituted ben-
zaldehydes proceeds smoothly to give homoallylic alcohols
without a promoter or catalyst. The R-hydroxyl ketones
are allylated in a highly chelation-controlled manner.
This selective system shows unique features: (a) no
Lewis acid capable of biligand for the chelation structure
is needed and (b) a hydroxyl group can be directly used
without protection for the chelation-controlled reaction.11
hydroxyl group acts by quenching the allylated stannox-
ide that is initially formed in either an intra- or inter-
molecular manner to form homoallylic alcohol. This
protonolysis step is thermodynamically very important
to complete the addition because of the reversibility of
the allylstannation of carbonyls.8,9
R ea ct ion s of Tet r a a llylt in w it h r-H yd r oxy- or
r-Meth oxyk eton es. Next, we investigated the reaction
of carbonyls bearing an alcoholic hydroxyl group. The
results of the allylation of 2-oxo-functionalized cyclohex-
anones 4 with tetraallyltin (1) are summarized in Scheme
1. High control of facial selectivity by the intramolecular
hydroxyl group (R ) H) was observed as was effective
enhancement of the reaction rate in either toluene or
MeOH, while methoxy-substituted ketone 4b showed low
selectivity. In particular, the reaction of 4a in MeOH
gave extremely high levels of selectivity and chemical
yield (>99% yield, 96% de).
These results are explained in Scheme 2. The allylic
tin species 1 generally adds in an equatorial direction to
the carbonyl groups in either form of cyclohexanone.10
Homoallylic alcohol 5 is the product via the chelation-
transition state X, where chelation contributes to a fast
addition rate (k1 > k2).11 The product distribution directly
depends on the kinetics (k1 vs k2) in MeOH because of
irreversible protonolysis into the products 5 and 6. The
reaction with hydroxyl ketone in toluene is also controlled
kinetically due to intramolecular protonolysis (7 f 8 or
10 f 11) to predominantly give chelation-controlled
product 5, although the reaction rate is considerably
slower than that in MeOH. On the other hand, the
reaction with methoxy ketone in toluene gave the product
under thermodynamic control, albeit in low efficiency due
to lack of the protonolysis step. The stronger interaction
between tin and the oxygen of OH compared to the
interaction between tin and the oxygen of OMe is
responsible for the higher selectivity of hydroxyketone
4a compared to methoxyketone 4b.
Exp er im en ta l Section
Gen er a l. IR spectra were recorded as thin films or as solids
in KBr pellets. 1H and 13C NMR spectra were obtained with
TMS as internal standard. Flash chromatography was per-
formed on silica gel. Bulb-to-bulb distillation (Kugelrohr) was
accomplished at the oven temperature and pressure indicated.
Yields were determined by GLC or 1H NMR using internal
standards.
Ma ter ia ls. Tetraallyltin (1) was prepared by known methods
from allyl Grignard reagent and tin tetrachloride.13 All alde-
hydes and ketones are commercial available.
Gen er a l P r oced u r e for Allyla tion of Ca r bon yls by Tet-
r a a llyltin . Tetraallyltin 1 (0.5 mmol) and a carbonyl compound
(2.0 mmol) were mixed in a solvent (2 mL) under the conditions
in text. To the reaction mixture, diethyl ether (30 mL) and
aqueous NH4F (15%; 15 mL) were added, and the resulting
Bu3SnF was filtered off. The filtrate was washed with water
(30 mL × 2), dried (MgSO4), and evaporated. Flash chroma-
tography and/or distillation gave pure products.
1-(2-Hyd r oxyp h en yl)-3-bu ten -1-ol (3b): bp 80 °C/ 3 mmHg;
IR (neat) 3200, 1600 cm-1 1H NMR (400 MHz, CDCl3) δ 7.99
;
(s, 1H), 7.20-6.81 (m, 4H), 5.90-5.73 (m, 1H), 5.25-5.19 (m,
2H), 4.90-4.85 (m, 1H), 2.77 (d, J ) 2.93 Hz, 1H), 2.67-2.56
(m, 2H); 13C NMR (22.6 MHz, CDCl3) δ 155.15, 133.83, 128.80,
127.03, 119.78, 117.00, 126.52, 118.98, 74.44, 42.03; MS m/z 164
(M+); HRMS calcd for C10H12O2 164.0837, found m/z 164.0844
(M+). Anal. Calcd for C10H12O2: C, 73.15; H, 7.37. Found: C,
72.94; H, 7.50.
This allylation system was applicable to acyclic sub-
strates as shown in Scheme 3. The hydroxyl ketone 12a
1-(3-Hyd r oxyp h en yl)-3-bu ten -1-ol (3c): mp 119 °C; IR
(KBr) 3330, 1640 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.24-7.19
(m, 1H), 6.92-6.86 (m, 2H), 6.76-6.73 (m, 1H), 5.86-5.75 (m,
1H), 5.20-5.13 (m, 2H), 5.02 (br, 1H), 4.70 (dd, J ) 7.81, 4.89
Hz, 1H), 2.57-2.43 (m, 2H), 2.07 (br, 1H); 13C NMR (100 MHz,
CDCl3) δ 155.72, 145.80, 134.28, 129.68, 118.58, 118.20, 114.46,
112.65, 73.00, 43.72; MS m/z 164 (M+); HRMS calcd for C10H12O2
164.0837, found m/z 164.0827 (M+). Anal. Calcd for C10H12O2:
C, 73.15; H, 7.37. Found: C, 73.06; H, 7.39.
(8) (a) Peruzzo, V.; Tagliavini, G. J . Organomet. Chem. 1978, 162,
37-44. (b) Gambaro, A.; Marton, D.; Peruzzo, V.; Tagliavini, G. J .
Organomet. Chem. 1981, 204, 191-196.
(9) We previously reported the allylation of carbonyls with dial-
lyldibutyltin in the presence of chlorotrimethylsilane. The formation
of a stable Si-O bond from Sn-O caused the shift of equilibrium to
the product, homoallyl silyl ethers, in excellent yields: Yasuda, M.;
Fujibayashi, T.; Shibata, I.; Baba, A.; Matsuda, H.; Sonoda, N. Chem.
Lett. 1995, 167-168.
(10) Naruta, Y.; Ushida, S.; Maruyama, K. Chem. Lett. 1979, 919-
922 and references therein.
(11) Chen, X.; Hortelano, E. R.; Eliel, E. L.; Frye, S. V. J . Am. Chem.
Soc. 1992, 114, 1778-1784.
(12) Sato, K.; Kira, M.; Sakurai, H. J . Am. Chem. Soc. 1989, 111,
6429-6431.
(13) Fishwick, M.; Wallbridge, G. H. J . Organomet. Chem. 1970, 25,
69-79.

Notes
J . Org. Chem., Vol. 63, No. 18, 1998 6403
Sch em e 2
observed at allylmethylene protons when 2-H was irradiated.;
13C NMR (22.6 MHz, CDCl3) δ 133.77, 118.37, 73.19, 73.04,
43.58, 34.22, 30.32, 23.31, 21.08; MS m/z 156 (M+); HRMS calcd
for C9H16O2 156.1150, found m/z 156.1151 (M+). Anal. Calcd
for C9H16O2: C, 69.19; H, 10.32. Found: C, 68.88; H, 10.31.
(1R*,2S*)-1-Allylcycloh exa n e-1,2-d iol (6a ). This minor
product is analyzed by selected NMR signals. 1H NMR (400
MHz, CDCl3) δ 5.96-5.85 (m, 1H), 5.22-5.16 (m, 2H), 3.59 (dd,
J ) 9.77, 4.40 Hz, 1H).
Sch em e 3
(1S*,2S*)-1-Allyl-2-m eth oxycycloh exa n -1-ol (5b): bp 100
°C/ 12 mmHg; IR (neat) 3450, 1640 cm-1 1H NMR (400 MHz,
;
CDCl3) δ 5.96-5.82 (m, 1H), 5.16-5.08 (m, 2H), 3.37 (s, 3H),
3.01 (dd, J ) 8.79, 3.91 Hz, 1H), 2.43-2.22 (m, 2H), 2.08 (br,
1H), 1.91-1.17 (m, 8H); 13C NMR (22.6 MHz, CDCl3) δ 134.05,
117.28, 81.85, 72.76, 56.30, 43.40, 34.22, 25.11, 22.73, 21.20; MS
m/z 170 (M+); HRMS calcd for C10H18O2 170.1307, found m/z
170.1297 (M+). Anal. Calcd for C10H18O2: C, 70.55; H, 10.66.
Found: C, 70.31; H, 10.69.
Sch em e 4
(1R*,2S*)-1-Allyl-2-m eth oxycycloh exa n -1-ol (6b). This
minor product is analyzed by selected NMR signals: 1H NMR
(400 MHz, CDCl3) δ 5.10-5.03 (m, 2H), 3.08 (dd, J ) 8.30, 3.42
Hz, 1H); 13C NMR (22.6 MHz, CDCl3) δ 134.71, 117.98, 84.07,
73.19, 56.66, 39.31, 33.80, 25.11, 22.03, 21.63.
(1S*,2R*)-1,2-Dip h en yl-4-p en ten e-1,2-d iol (13a ): mp 96-
97 °C; IR (KBr) 3450 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.25-
6.95 (m, 10H), 5.63-5.52 (m, 1H), 5.19-5.08 (m, 2H), 4.81 (d, J
) 4.40 Hz, 1H), 2.96 (dd, J ) 14.16, 5.86 Hz, 1H), 2.78 (dd, J )
14.16, 8.79 Hz, 1H), 2.71 (d, J ) 4.40 Hz, 1H), 2.58 (s, 1H); 13C
NMR (100 MHz, CDCl3) δ 141.45, 139.34, 133.27, 127.74, 127.47,
127.32, 126.75, 126.49, 119.49, 80.29, 78.32, 42.44; MS m/z 237
(M+ - 17). Anal. Calcd for C17H18O2: C, 80.28; H, 7.13.
Found: C, 79.89; H, 7.16. The relative configuration was
determined by X-ray analysis (see Supporting Information).
(1S*,2S*)-1,2-Dip h en yl-4-p en ten e-1,2-d iol (14a ). This mi-
nor product is analyzed by selected NMR signals: 1H NMR (400
MHz, CDCl3) δ 5.73 (ddt, J ) 17.09, 10.25, 7.32 Hz, 1H), 5.13-
4.99 (m, 2H), 4.81 (d, J ) 4.40 Hz, 1H), 3.13 (dd, J ) 13.67, 7.32
Hz, 1H), 2.97 (dd, J ) 13.67, 7.32 Hz, 1H); 13C NMR (100 MHz,
CDCl3) δ 141.63, 138.73, 133.27, 120.19, 81.37, 78.43, 43.85.
(1S*,2R*)-1-Meth oxy-1,2-diph en yl-4-pen ten -2-ol (13b): mp
1-(2-Meth oxyp h en yl)-3-bu ten -1-ol (3d ): bp 75 °C/ 3 mmHg;
IR (neat) 3300, 1600 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.35-
6.87 (m, 4H), 5.85 (ddt, J ) 17.09, 10.26, 7.08 Hz, 1H), 5.14 (d,
J ) 17.09 Hz, 1H), 5.10 (d, J ) 10.26 Hz, 1H), 4.96 (br, 1H),
3.86 (s, 3H), 2.63-2.47 (m, 3H); 13C NMR (22.6 MHz, CDCl3) δ
156.12, 135.05, 131.76, 128.04, 126.58, 120.51, 117.22, 110.29,
69.32, 55.14, 41.81; MS m/z 178 (M+); HRMS calcd for C11H14O2
178.0994, found m/z 178.0977 (M+).
1-(3-Meth oxyp h en yl)-3-bu ten -1-ol (3e): bp 90 °C/ 3 mmHg;
IR (neat) 3400, 1640 cm-1; 1H NMR (400 MHz, CDCl3) δ 7.29-
7.24 (m, 1H), 6.95-6.93 (m, 2H), 6.84-6.80 (m, 1H), 5.81 (ddt,
J ) 17.09, 10.25, 7.08 Hz, 1H), 5.20-5.13 (m, 2H), 4.72 (dd, J )
7.81, 4.88 Hz, 1H), 3.82 (s, 3H), 2.57-2.44 (m, 2H), 2.04 (br, 1H);
13C NMR (22.6 MHz, CDCl3) δ 159.51, 145.54, 134.35, 129.23,
118.01, 118.01, 112.86, 111.27, 73.19, 55.11, 43.64; MS m/z 178
(M+); HRMS calcd for C11H14O2 178.0994, found m/z 178.1001
(M+).
1
47 °C; IR (KBr) 3500, 1640 cm-1; H NMR (400 MHz, CDCl3) δ
7.25-6.95 (m, 10H), 5.63 (dddd, J ) 17.09, 10.25, 7.57, 6.60 Hz,
1H), 5.10 (d, J ) 17.09 Hz, 1H), 5.02 (d, J ) 10.25 Hz, 1H), 4.29
(s, 1H), 3.25 (s, 3H), 2.91-2.81 (m, 3H); 13C NMR (100 MHz,
CDCl3) δ 141.99, 136.65, 133.67, 128.49, 128.37, 127.47, 127.27,
126.64, 126.40, 118.35, 89.51, 78.04, 57.24, 42.64; MS m/z 227
(M+ - 41); HRMS calcd for C18H20O2 269.1533, found m/z
269.1541 (M+ + 1). Anal. Calcd for C18H20O2: C, 80.56; H, 7.51.
(1S*,2S*)-1-Allylcycloh exa n e-1,2-d iol (5a ): mp 75 °C; IR
(KBr) 3420, 3300, 1640 cm-1; 1H NMR (400 MHz, CDCl3) δ 5.90
(ddt, J ) 16.85, 10.63, 7.70 Hz, 1H), 5.15 (d, J ) 10.62 Hz, 1H),
5.14 (d, J ) 16.85 Hz, 1H), 3.45 (dd, J ) 9.35, 3.85 Hz, 1H),
2.40 (ddt, J ) 13.56, 7.69, 1.10 Hz, 1H), 2.29 (ddt, J ) 13.56,
7.69, 1.10 Hz, 1H), 1.94 (br, 2H), 1.77-1.23 (m, 8H); NOE was

6404 J . Org. Chem., Vol. 63, No. 18, 1998
Notes
Found: C, 80.30; H, 7.55. The relative configuration was
determined by X-ray analysis (see Supporting Information).
(1S*,2S*)-1-Met h oxy-1,2-d ip h en yl-4-p en t en -2-ol (14b ).
This minor product is analyzed by selected NMR signals: 1H
NMR (400 MHz, CDCl3) δ 5.57 (dddd, J ) 17.09, 10.25, 7.56,
6.35 Hz, 1H), 5.01 (d, J ) 17.09 Hz, 1H), 4.98 (d, J ) 10.25 Hz,
1H), 4.28 (s, 1H), 3.22 (s, 3H), 2.91 (br, 1H), 2.68 (dd, J ) 14.16,
6.35 Hz, 1H), 2.56 (dd, J ) 14.16, 7.56 Hz, 1H); 13C NMR (100
MHz, CDCl3) δ 141.99, 136.65, 133.67, 128.49, 128.37, 127.47,
127.27, 126.64, 126.40, 118.35, 89.51, 78.04, 57.24, 42.64.
Sports, and Culture, of the J apanese Government.
Thanks are due to Mr. H. Moriguchi, Faculty of Engi-
neering, Osaka University, for assistance in obtaining
MS spectra.
Su p p or tin g In for m a tion Ava ila ble: Details of X-ray
sturcture analyses of compounds 13a and 13b (36 pages). This
material is contained in libraries on microfiche, immediately
follows this article in the microfilm version of the journal, and
can be ordered from the ACS; see any current masthead page
for ordering information.
Ack n ow led gm en t. This work was supported by a
Grant-in-Aid for Scientific Research on Priority Area No.
10125224 from the Ministry of Education, Science,
J O9805697