Highly efficient catalytic synthesis of substituted allenes using indium

Article abstract of DOI:10.1002/1521-3773(20021018)41:20<3901::AID-ANIE3901>3.0.CO;2-S

Versatile, convenient, mild: Allenylindium intermediates generated from the reaction of indium with propargyl bromides were employed as effective coupling partners in Pd-catalyzed cross-coupling reactions with a variety of electrophiles to produce allenes, polyallenes, and unsymmetrical bis(allenes) in excellent yields with complete regioselectivity and chemoselectivity (see scheme for one example).

Full text of DOI:10.1002/1521-3773(20021018)41:20<3901::AID-ANIE3901>3.0.CO;2-S

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17.4 ppm; b) 11: m.p. 778C; [a]D25 ¼ À157.6 (c ¼ 1.02 in CHCl3); 1H NMR
(400 MHz, CDCl3): d ¼ 4.12 4.08 (m, 2H; CH,CHH), 3.94 (dd, J ¼ 12.0,
5.0 Hz, 1H; CHH), 3.76 (s, 3H; CO2CH3), 3.28 (s, 3H; OCH3), 3.26 (s,
3H; OCH3), 1.32 (s, 3H; CCH3), 1.27 ppm (s, 3H; CCH3); 13CNMR
(100 MHz, CDCl3): d ¼ 171.0, 99.6, 98.7, 68.1, 57.7, 51.9, 50.0, 48.2, 17.9,
17.7 ppm; c) 12: m.p. 778C; [a]D25 ¼ À266.5 (c ¼ 1.6 in CHCl3); 1H NMR
(400 MHz, CDCl3): d ¼ 9.73 (s, 1H; CHO), 4.07 (d, J ¼ 11.6 Hz, 1H;
CHH), 3.91 3.86 (m, 1H; CHH), 3.77 (d, J ¼ 4.4 Hz, 1H; CH), 3.38 (s,
3H; OCH3), 3.28 (s, 3H; OCH3), 1.37 (s, 3H; CCH3), 1.24 ppm (s, 3H;
C(CH3)); 13C NMR (100 MHz, CDCl3): d ¼ 201.2, 99.4, 98.5, 74.6, 55.6,
50.3, 48.2, 17.8, 17.7 ppm.
Scheme 1. Palladium-catalyzed cross-coupling reaction mediated by in-
dium. Tf ¼ trifluoromethanesulfonyl.
[Pd(PPh3)4] in the presence of 3 equivalents of LiI in DMF at
1008C under a nitrogen atmosphere (see Experimental
Section), and 1-allenylnaphthalene was produced in quanti-
tative yield (98%) with complete regioselectivity (Table 1,
entry 1). The allenylindium reagent generated in situ from the
reaction of 1 equivalent of indium with 1.5 equivalents of
propargyl bromide gave the best results as a coupling
partner.[9]
[8] a) H. S. Isbell, H. L. Frush, Carbohydr. Res. 1979, 72, 301 304; b) C. C.
Wei, S. De Bernardo, J. P. Tengi, J. Borgese, M. Weigele, J. Org. Chem.
1985, 50, 3462 3467; c) E. Abushanab, P. Vemishetti, R. W. leiby, H. K.
Singh, A. B. Mikkilineni, D. C.-J. Wu, R. Saibaba, R. P. Panzica, J. Org.
Chem. 1988, 53, 2598 2602.
[9] CCDC-186381 to CCDC-186386 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ,
UK; fax: (þ 44)1223-336-033; or deposit@ccdc.cam.ac.uk).
To demonstrate the efficiency and scope of the present
method, we applied this catalytic system to a variety of
propargyl halides and organic electrophiles. For the propargyl
halides as coupling partners, the presence of various alkyl
substituents at the a and g positions had little effect on either
the reaction rate or the product yield (Table 1). Under the
optimized conditions, treatment of iodobenzene with 3-
bromo-1-phenyl-1-butyne and indium gave selectively trisub-
stituted allene 2 in 80% yield (entry 2). Varying the electron
demand of the substituents on the arene did not diminish the
efficiency and selectivity (entries 3, 7 9). It is noteworthy that
protection of an oxo group and a hydroxy group on substrates
is not necessary, as demonstrated by the reactions of 4-
iodoacetophenone (entry 5) and 3-iodophenol (entry 6), re-
spectively. Hetero substituents turned out to be compatible
with the reaction conditions (entry 10). The method worked
equally well with vinyl halides (entries 11 and 12) and imidoyl
bromide (entry 13). Treatment of iodophenylacetylene with
allenylindium produced 3-methyl-1-phenyl-3,4-pentadien-1-
yne (14) in 91% yield (entry 14). In the case of vinyl triflate,
the desired product 15 was obtained in 90% yield (entry 15).
Surprisingly, no propargylic cross-coupling product is formed
in any reactions.
Highly Efficient Catalytic Synthesis of
Substituted Allenes Using Indium**
Kooyeon Lee, Dong Seomoon, and Phil Ho Lee*
Since allenes are versatile building blocks both for organic
synthesis[1] and in transition-metal-promoted carbon carbon
bond-forming reactions,[2] development of practical methods
for their preparation is of great interest. Allene moieties can
be prepared by alkylation of allenylmethyl halides with an
appropriate carbanionic species,[1e] by SN2’-type selective
displacement of propargyl alcohol derivatives with organo-
copper reagents,[1e,3] and by intramolecular regio-and stereo-
selective reduction of alkynes.[4] The synthesis of allenes by
metal-catalyzed cross-coupling reactions is an alternative
method;[5] however, some disadvantages are the inconvenient
preparation of the reagents, limited substrate scope, and
incompatibility of sensitive groups to the reaction condi-
tions.[6] Recently, several reports have described the synthesis
of allenes with transition metal complexes.[5] Despite this
recent progress a method for the highly efficient and catalytic
synthesis of substituted allenes is still needed. We have
realized this goal (Scheme 1) as part of our continuing studies
We then applied the present method to polyhalogenated
aromatic compounds to obtain polyallenyl-substituted arenes,
which can be used effectively in material and polymer
sciences. Reaction of 4,4’-diiodobiphenyl with two equivalents
of allenylindium produced 4,4’-diallenylbiphenyl 16 in 90%
yield [Eq. (1)]. We were pleased to observe that treatment of
directed toward the development of efficient indium-medi-
[8]
ated reactions.[7]
,
The catalytic activity of several palladium complexes was
initially examined in the reaction of 1-iodonaphthalene with
allenylindium. The best results were obtained with 4 mol%
[*] Prof. Dr. P. H. Lee, K. Lee, D. Seomoon
Department of Chemistry, Kangwon National University
Chunchon 200-701 (Korea)
Fax : (þ 82)33-253-7582
E-mail: phlee@kangwon.ac.kr
[**] This work was supported financially by the CMDS at KAIST. We
thank Prof. Sunggak Kim and Prof. Sukbok Chang of KAIST for
helpful discussions and Hyosoon Ahn, Keuckchan Bang, and Dr. Sun-
young Sung for the preparation of starting materials and preliminary
experiments.
1,3,5-tribromobenzene with 1-bromo-2-butyne and indium
selectively gave 1,3,5-tri(1’-methylallenyl)benzene (17) in
70% yield [Eq. (2)]. On the basis of these results, unsym-
Angew. Chem. Int. Ed. 2002, 41, No. 20
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Table 1. Palladium-catalyzed cross-coupling reactions of in-situ-generated allenylindium reagents with organic acceptors.
Entry
Acceptor
R1
R2
R3
Product
Yield [%][a]
98
97[b]
1
H
H
H
22[c](58)[d]
97[e]
84[f]
2
3
Ph
Me
H
H
H
80
91
[g]
THPOCH2
4
5
H
H
H
H
Me
H
90
87[b]
6
H
H
H
90[b]
91[b]
66[f]
7
8
H
H
H
H
H
Ph
90
96
9
Et
H
H
10
11
12
Me
Me
Me
H
H
H
H
H
H
92
91
90
13
14
15
H
H
H
H
H
H
H
86[b]
91
Me
H
90[b]
[a] Yield of isolated product. The reaction was performed in the presence of 4 mol% [Pd(PPh3)4] and 3 equiv LiI in DMF at 1008C; allenylindium was
obtained from the reaction of 1 equiv indium with 1.5 equiv propargyl bromide unless otherwise noted. [b] 3 Equiv LiCl was used. [c] 1 Equiv LiCl was used.
[d] Yield of recovered 1-iodonaphthalene. [e] LiBr was used. [f] THF was used as a solvent. [g] THP ¼ tetrahydropyranyl.
metrical bis(allenes) 18 and 19 were prepared chemoselectively
and regioselectively in one pot from 4-bromoiodobenzene and
2,5-dibromopyridine in good yields [Eqs. (3) and (4)].
Iodobenzene was treated with 1-bromo-2,7-octadiyne and
indium to produce allenyne 20 in 92% yield, which is a
useful compound in palladium-catalyzed carbocyclization
[Eq. (5)].[2p] Interestingly, the double cross-coupling reaction
of two equivalents of ethyl 4-iodobenzoate with one equiv-
alent of 1,10-dibromo-2,8-decadiyne in the presence of indium
yielded bis(allene) 21 in 68% yield [Eq. (6)].[2o]
In conclusion, we have demonstrated for the first time that
allenylindium reagents generated in situ from the reaction of
3902
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indium with propargyl bromides can be employed as effective
cross-coupling partners in palladium-catalyzed cross-coupling
reactions with a variety of organic electrophiles to produce
substituted allenes, polyallenes, and unsymmetrical bis(al-
lenes) in excellent yields with complete regioselectivity and
chemoselectivity.
[6] J. A. Marshall, X. Wang, J. Org. Chem. 1992, 57, 1242, and references
therein.
[7] a) P. H. Lee, K. Bang, K. Lee, C.-H. Lee, S. Chang, Tetrahedron Lett.
2000, 41, 7521; b) P. H. Lee, K. Bang, H. Ahn, K. Lee, Bull. Korean
Chem. Soc. 2001, 22, 1385; c) P. H. Lee, S. Seomoon, K. Lee, Bull.
Korean Chem. Soc. 2001, 22, 1380; d) P. H. Lee, K. Lee, S.-Y. Sung, S.
Chang, J. Org. Chem. 2001, 66, 8646; e) P. H. Lee, K. Lee, S. Kim, Org.
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[8] For some previously reported examples of indium-mediated cross-
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Experimental Section
Typical experimental procedure: 1-Iodonaphthalene (127.0 mg, 0.5 mmol)
was added at room temperature under a nitrogen atmosphere to a
suspension of [Pd(PPh3)4] (23.1 mg, 4 mol%) and lithium iodide (200.8 mg,
1.5 mmol) in DMF (1 mL). After 15 min the allenylindium reagent, which
was generated from propargyl bromide (89.2 mg, 0.75 mmol) and indium
(57.0 mg, 0.5 mmol) in DMF (1 mL), was added, and the mixture was
stirred at 1008C for 1 h. The reaction mixture was quenched with saturated
aqueous NaHCO3. The aqueous layer was extracted with diethyl ether (3 î
20 mL), and the combined organic solvents were washed with water and
brine, dried with MgSO4, filtered, and concentrated under reduced
pressure. The residue was purified by silica gel column chromatography
with n-hexane to give 1-allenylnaphthalene (81.3 mg, 98%).
Received: June 6, 2002 [Z19484]
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4.94 ppm (t, J ¼ 7.11 Hz, 1H). 13C NMR (100 MHz, [D7]DMF, 258C)
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