Efficient synthesis of homoallylic alcohols/amines from allyltributylstannane and carbonyl compounds/imines using iodine as catalyst under acetic acid-water medium

Article abstract of DOI:10.1080/00397911.2015.1085574

This paper describes a general method for the synthesis of homoallylic alcohols and amines by nucleophilic addition reaction of allyltributylstannane to carbonyl compounds and aldimines where iodine acts as a catalyst in H2O/acetic acid (1:1) medium. Only 10 mol% of I2 is required for various organic transformations. By using this process, various homoallylic alcohols and amines are produced in good to excellent yields.

Full text of DOI:10.1080/00397911.2015.1085574

Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic
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ISSN: 0039-7911 (Print) 1532-2432 (Online) Journal homepage: http://www.tandfonline.com/loi/lsyc20
Efficient Synthesis of Homoallylic Alcohols/
Amines from Allyltributylstannane and Carbonyl
Compounds/Imines Using Iodine as Catalyst Under
Acetic Acid–Water Medium
Pabitra Kumar Kalita, Susanta Kumar Borthakur, Runumi Das & Chandan
Jyoti Choudhury
To cite this article: Pabitra Kumar Kalita, Susanta Kumar Borthakur, Runumi Das &
Chandan Jyoti Choudhury (2015): Efficient Synthesis of Homoallylic Alcohols/Amines from
Allyltributylstannane and Carbonyl Compounds/Imines Using Iodine as Catalyst Under Acetic
Acid–Water Medium, Synthetic Communications, DOI: 10.1080/00397911.2015.1085574
To link to this article: http://dx.doi.org/10.1080/00397911.2015.1085574
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Date: 21 September 2015, At: 01:19

Efficient Synthesis of Homoallylic Alcohols/Amines from Allyltributylstannane and
Carbonyl Compounds/Imines Using Iodine as Catalyst Under Acetic Acid–Water
Medium
Pabitra Kumar Kalita1, Susanta Kumar Borthakur1, Runumi Das1, Chandan Jyoti
Choudhury1
1Department of Chemistry, Arya Vidyapeeth College, Guwahati, Assam, India
E-mail: pk80chem@yahoo.com
Abstract
This paper describes a general method for the synthesis of homoallylic alcohols and
amines by nucleophilic addition reaction of allyltributylstannane to carbonyl compounds
and aldimines where iodine acts as a catalyst in H2O:acetic acid (1:1) medium. Only 10
mol % of I2 is required for various organic transformations. By using this process, various
homoallylic alcohols and amines are produced in good to excellent yield.
KEYWORDS: Allylation, Carbonyl compounds, Aldimines, Iodine
INTRODUCTION
Allylation of carbonyl compounds and aldimines to produce homoallylic alcohols and
amines respectively has been widely investigated and established a powerful tool to
synthesize valuable intermediates such as β-hydroxy carbonyl compounds, β- and γ-
amino acids, spiro cyclic compounds and γ-lactams. They have attracted significant
1

attention due to their versatile uses as important building blocks for natural product
synthesis.[1] Hence, numerous reagents and methods have been developed to accomplish
this transformation.[2] A number of methods have been developed for allylation reaction
involving various metals[3] such as zinc, tin, indium, bismuth, manganese, magnesium,
antimony, scandium, cobalt, cerium and silver. Wolinsky and his co-workers[4] reported
the allylation of aldehydes and ketones with allyl bromide mediated by ‘activated’ zinc
dust in 95% ethanol at 78 oC. Araki et al. reported the allylation of carbonyl compounds
using indium metal in an anhydrous organic solvent.[5] Later, Li and Chan successfully
carried out the indium-mediated, Barbier-type allylation in aqueous medium.[6] Nokami et
al. [7] observed that water had an accelerating effect on the allylation of carbonyl
compounds with diallyltin dibromide in ether. Chen[8] reported Sb-mediated allylation in
alcohol-water mixture. Jarvo et al.[9] reported silver bromide catalyzed allylation of
aldehydes and ketones using unactivated manganese powder. In the same year Wu and
Sun[10] reported the facile allylation of N-Boc and N-Cbz imines by using
allyltrichlorosilane promoted by DMF and acetonitrile at 0 °C. Wang[11] and his co-
workers used tin nano particles for the allylation of aldehydes and ketones in aqueous
medium. Slaton et al.[12] reported tin mediated Barbier-type allylation in ionic liquids. In
the same year, Li and his co-workers[13] reported a mild and efficient allylation reaction
mediated by magnesium powder under solvent-free conditions. Guo et al.[14] reported a
method for the allylation reaction of the carbonyl compounds using 2 molar eqiv. of Cu
powder to accomplish the product formation. Bellucci et al.[15] developed a method for
the allylation of imines promoted by lanthanide triflates. One year later, Wang[16] and his
co-workers reported that imines can be allylated by magnesium or zinc mediated Barbier-
2

type procedure to produce homoallylamines in excellent yields. Phukan[17] reported that
only 10 mol% iodine catalyzes efficiently the three-component reaction of aldehydes,
benzyl carbamate and allyltrimethylsilane to afford the corresponding protected
homoallylamine in good to excellent yield. Yadav et al.[18] reported the allylation and
alkynylation of cyclic allylic acetates with allyltrimethylsilane and alkynyl silanes in the
presence of molecular iodine in dichloromethane at rt. Although a number of allylating
reagents are used for the allylation reaction, allyltributylstannane is one of the most
common reagents used for the synthesis of homoallylic alcohols and amines. Generally,
strong Lewis acids such as TiCl4 and BF3. OEt2 and other metal complexes such as
PdCl2(PPh3)2, PtCl2(PPh3)2, bis-π-allyl palladium complex, lanthanide salts and LiClO4
are used for the preparation of homoallylic amines.[19] However, in most of allylation
reactions of carbonyl compound, either low yield[12, 14] or prolonged reaction time[9] is
needed. Also, metal triflates are highly expansive.[15] Therefore, the development of
novel, common, cheap, high yielding and useful catalytic methods is of interest. Iodine
has emerged as a very effective catalyst for various organic transformations.[20] In
continuation of our work on various allylation reaction,[21] we wish to report herein a
method for the synthesis of hommoallylic alcohols and amines by nucleophilic addition
reaction of allyltributylstannane to carbonyl compounds and aldimines using I2 as catalyst
in the presence H2O:acetic acid (1:1) (Scheme 1).
RESULTS AND DISCUSSION
In a typical reaction, aldehydes (1 mmol), allyltributylstannane (1 mmol) and I2 (5 mol
%) were added successively in H2O:acetic acid (1:1; 1 mL) at room temperature. The
3

reaction was monitored by TLC. The results are presented in Table 1. Initial experiment
without acetic acid failed to produce any product at room temperature (Table 1, entry 1).
Another experiment without both H2O and the catalyst also produced negative result
(Table 1, entry 2 and 3 respectively). When the reaction was examined using iodine as
catalyst (5 mol%), in a mixed solvent system H2O-acetic acid at the ratio of 1:1, it
produced 58% of the product formation after 1 h at room temperature (Table 1, entry 4).
The reaction with increasing the concentration of the catalyst as well as
allyltributylstannane gradually increases the yield of the reaction up-to 95%. However,
the reaction showed positive results when we examined the reaction by using some Lewis
acid e.g. CuI and FeCl3 as catalyst where the corresponding homoallyl alcohols produced
moderate to low yield respectively (Table 1, entry 14 and 15). The reaction was also
examined using different solvents such as THF, CH3CN, DMF, DMSO and CH2Cl2
(Table 1, entries 9–13). But, in every cases, the reaction was found to be inactive for
product formation. Finally, the use of 10 mol % of I2, 1.2 equiv of allyltributylstannane
and 1 equiv of benzaldehyde in H2O:acetic acid (1:1; 1 mL), was found to be optimum to
realize the best yield of the product.
After establishing the optimized reaction conditions, a variety of aromatic and aliphatic
aldehydes were investigated under the same reaction conditions. The results are
summarized in Table 2. In general, the procedure works well for a variety of aliphatic as
well as aromatic aldehydes to produce the corresponding homoallylalcohols in excellent
yield. Substituted aromatics bearing the groups –Cl, -OMe, -Br, -NO2, -CH3 reacted very
successfully no matter the substituent position in the aromatic ring produced high yields.
4

The success of the homoallylation of the aldehydes prompted us to extend the procedure
to ketones (Table 2, entry 13-18) and aldimines (Table 3) which were produced in situ of
the reaction between aldehydes and amines. Initial experiment with acetophenone
produces 76 % yield after 2 h (Table 2, entry 13) of the reaction time. The reaction was
further extended to a variety of ketones in which cases both aromatic, cyclic and aliphatic
ketones produces excellent yield with slightly longer reaction time.
CONCLUSION
In summary, we have developed a method for allylation reaction of aldehydes, ketones
and imines with allyltributylstannane in acetic acid-water medium. The advantages of
these methods include the use of a nontoxic catalyst, easy to handle and the generation of
homoallyl alcohol and amine in one step. Further investigation regarding the asymmetric
version of this reaction in the same solvent system is currently in progress in our
laboratory.
EXPERIMENTAL
All the chemicals used were of analytical grade. 1H and 13C NMR spectra were obtained
in CDCl3 at 300 and 75 MHz respectively, using Bruker Ultrashild 300 MHz
spectrometer (TMS as internal reference). Mass spectra were recorded on a Perkin Elmer
Clarus 600 C mass spectrometer. IR spectra were recorded by using Perkin Elmer
Spectrum RX IFT-IR Spectrometer.
5

Synthesis Of 1-Phenyl-But-3-En-1-Ol
A mixture of benzaldehyde (106 mg,1 mmol), allyltributylstannane (397 mg, 1.2 mmol)
and I2 (25.3 mg, 0.1 mmol) were added in H2O:AcOH (1:1, 1 mL), at room temperature.
After stirring the reaction for appropriate time (checked by TLC) the solution was added
to water and the reaction mixture was extracted with diethylether (3 x 10 mL). The
combined organic extract was dried over sodium sulphate, filtered and concentrated. The
crude product was purified by flash column chromatography over silica gel (230-400
mesh) using ethylacetate-petroleum ether (5:95) as eluent.
1-Phenyl-but-3-en-1-ol (3a). IR (υ/cm-1): 3372, 3073, 2907, 1641, 1493, 1445, 1043; 1H
NMR (300 MHz, CDCl3): δ 7.43-7.23 (m, 5H), 5.91-5.72 (m, 1H), 5.24-5.11 (m, 2H),
4.80-4.70 (m, 1H), 2.60-2.45 (m, 2H), 2.00 (s, 1H); 13C NMR (75 MHz, CDCl3): δ 143.8,
134.4, 128.4, 127.5, 125.8, 118.5, 73.3, 43.8; ESIMS (m/z) 149 [M+H]+
.
Benzyl-(1-phenyl-but-3-enyl)-amine (6a). IR (υ/cm-1): 3460, 3058, 2921, 1489; 1H
NMR (300 MHz, CDCl3): δ 7.97-7.01 (m, 9H), 5.80-5.60 (m, 1H), 5.18-4.92 (m, 2H),
4.22-4.10 (m, 1H), 3.46 (d, J = 12 Hz, 1H), 3.40 (d, J = 12 Hz, 1H), 2.60 (s, 1H, NH),
2.40-2.10 (m, 2H); ESIMS (m/z) 238 [M+H]+.
ACKNOWLEDGEMENTS
Financial support from UGC, New Delhi (Grant No: F. 5-233/2011-12/MRP/ NERO/
10756) is gratefully acknowledged.
6

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Bissett, J. S.; Greeves, N.; Levin, D. Three component synthesis of homoallylic amines.
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10

SnCl2·2H2O-mediated Barbier-type allylation: A comparative evaluation of the catalytic
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11

Table 1 Synthesis of homoallylic alcohols from Benzaldehydes using I2 as a catalyst.
Entry PhCHO Solvent
Acetic
Allyl tributylstannane Catalyst
Time Yielda
(mmol)
(mL)
acid (mL) (mmol)
(mol%)
I2 (5)
(h)
24
24
24
1
(%)
0
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
H2O (1)
-
-
1
2
1
1
1
1
1
1
1
-
1
I2 (5)
0
3
H2O (1)
H2O (1)
H2O (1)
H2O (1)
H2O (1)
H2O (1)
THF (1)
1
-
0
4
1
I2 (5)
58
82
80
90
95
0
5
1.1
1
I2 (5)
1
6
I2 (10)
I2 (5)
1
7
1.1
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1
I2 (10)
I2 (10)
I2 (10)
I2 (10)
I2 (10)
I2 (10)
CuI (10)
FeCl3(10)
8
1
9
24
24
24
24
24
1
10
11
12
13
14
15
CH3CN (1) -
0
DMF(1)
-
-
0
DMSO (1)
0
CH2Cl2 (1) -
0
H2O (1)
H2O (1)
1
40
10
1
1
aisolated yield after chromatographic purification
12

Table 2 Acetic acid:H2O mediated and I2 catalyzed allylation of aldehydesa
Entry Aldehydes/Ketones Productb
1
Time(h) Yield(%)c
1.0
95
2
3
4
1.0
1.0
1.0
83
88
92
5
6
1.0
1.0
76
87
7
8
1.0
1.0
85
93
13

9
1.0
1.0
88
83
10
11
12
2.0
2.0
79
82
13
14
2.0
2.2
76
93
15
2.0
83
16
17
2.5
2.2
85
83
14

18
2.5
82
aReaction condition: Aldehydes/Ketones, 1 mmol; Allyltributylstannane, 1.2 mmol;
H2O:AcOH = 1:1; I2, 10 mol %
bAll products were characterized by IR, 1H NMR and 13C NMR.
c Isolated yield after chromatographic purification.
15

Table 3 I2 catalyzed three-component synthesis of homoallylic aminesa
Entry Reactant
1
Productb
Time (h) Yield (%)c
2.0
83
2
3
4
2.5
92
2.0
2.0
73
84
5
6
2.0
2.5
77
88
7
2.5
89
16

8
2.0
2.0
2.5
82
9
81
10
Trace
aReaction condition: Aldehyde, 1mmol; benzylamine, 1 mmol; allyltributyltin, 1.2 mmol;
H2O:AcOH = 1:1; I2, 10 mol %.
bAll products were characterized by IR, 1H NMR and 13C NMR.
cIsolated yield after chromatographic purification.
17

Scheme 1
18