New versions of Pd0-catalyzed allylation of C-nucleophiles

Article abstract of DOI:10.1007/s11172-006-0555-x

New "one-pot" protocols proposed for Pd⁰-catalyzed allylation of C-nucleophiles involve deprotonation of the corresponding CH acids with in situ generated dialkylamide and alkoxide anions.

Full text of DOI:10.1007/s11172-006-0555-x

Russian Chemical Bulletin, International Edition, Vol. 55, No. 11, pp. 2103—2105, November, 2006
2103
Brief Communications
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New versions of Pd ꢀcatalyzed allylation of Cꢀnucleophiles*
A. V. Lozanova, T. M. Ugurchieva, and V. V. Veselovskyꢀ
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
4
7 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 5328. Eꢀmail: ves@ioc.ac.ru
0
New "oneꢀpot" protocols proposed for Pd ꢀcatalyzed allylation of Сꢀnucleophiles involve
deprotonation of the corresponding СH acids with in situ generated dialkylamide and alkoxide
anions.
0
Key words: allylation, Сꢀnucleophiles, Pd complex.
Palladiumꢀcatalyzed allylation of Сꢀnucleophiles is
an efficient tool for С—С bonding (see Ref. 1). The most
commonly used allylating reagents are allylic acetates.
The reaction is usually preceded by generation of the
carbanion from a CH acid via deprotonation with a base
into a dialkylamide, which deprotonates a C—H acid,
thus ensuring recycling of the amine. Allylation of diethyl
malonate with allyl acetate 1 under these conditions gave
diethyl allylmalonate 2 in 65% yield.*
To find out whether it is possible to carry out asymꢀ
metric synthesis, we performed allylation of diethyl
malonate with acetate 3 in the presence of optically active
amine 5. However, the product 4 obtained in 87% yield
exhibited no noticeable optical activity.
(
e.g., NaH). The resulting solution is transferred to a reꢀ
0
action vessel with a separately prepared Pd complex. The
2
0
use of allyl carbonates, which react with Pd to generate
in situ a (πꢀallyl)palladium complex and, simultaneously,
an alkoxide anion, allows "one pot" reactions. Here we
report on a new version of the "one pot" reaction that
involves two parallel catalytic cycles for the formation of
a Сꢀnucleophile and a (πꢀallyl)palladium complex. One
cycle is based on the known synthesis of lithium dialkylꢀ
amides from secondary amines and metallic lithium in
For the same purpose, we attempted to modify the
2
aforementioned method by replacing achiral allyl carꢀ
bonate in this process by optically active compound 6
(under the assumption of possible asymmetric induction
during the formation of metal complex 7 in the allylation
of prochiral СН acid 8 (Scheme 2)).
This reaction smoothly occurred at 30 °С to give alꢀ
lylic derivative 9 in 85% yield. However, compound 9 was
optically inactive.
3
the presence of electron acceptors, e.g., αꢀmethylstyrene
(
Scheme 1). According to the proposed procedure,
1
0 mol.% of the amine is used. This is converted in situ
*
Dedicated to Academician O. M. Nefedov on the occasion of
* In the absence of an amine, diethyl allylmalonate did not form
under the conditions studied.
his 75th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2024—2026, November, 2006.
066ꢀ5285/06/5511ꢀ2103 © 2006 Springer Science+Business Media, Inc.
1

2104
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 11, November, 2006
Lozanova et al.
Scheme 1
spectrometer in CDCl with reference to the signals of the solꢀ
3
vent. Mass spectra (EI, 70 eV) were recorded on a Finnigan
MAT ITDꢀ700 instrument. R values were determined on Silufol
f
plates with the fixed SiO layer.
2
Column chromatography was carried out on Silicа gеl 60
0.04—0.06 mm; Fluka).
(
Solvents were purified and dried according to standard proꢀ
cedures. Light petroleum (b.p. 40—70 °С) was used. The Aldrich
chemicals we used were Pd (dba) (CHCl ) (dba is dibenzylꢀ
2
3
3
ideneacetone), 1,2,5,6ꢀdiꢀOꢀisopropylideneꢀαꢀDꢀglucofuranose,
allyl chloroformate, and TMEDA.
4
(
±)ꢀ3ꢀAcetoxyꢀ1,3ꢀdiphenylpropꢀ1Eꢀene (3) and [tertꢀbuꢀ
5
18
tyl(diphenyl)silyl][1(R)ꢀphenylethyl]amine (5) ([α]D +70.6
(
с 1.02, СHCl )) were prepared according to known procedures.
3
Diethyl allylmalonate (2). Triphenylphosphine (68 mg,
.26 mmol) was added at 25 °С to a stirred suspension (argon) of
Pd (dba) (CHCl ) (27 mg, 0.025 mmol) in THF (4 mL). After
0
2
3
3
3
0 min, AllOAc (200 mg, 2 mmol) was added. After 10 min, the
following reagents were successively added to the resulting soluꢀ
tion in the order of appearance: diethyl malonate (320 mg,
2 mmol), finely sliced Li foil (14 mg, 2 mgꢀat.), HN(SiMe3)2
i. Pd (dba) •CHCl —PPh (1.25 mol.%);
Li — PhC(Me)=CH2 — HNR2 (10 mol.%), THF.
2
3
3
3
(
32 mg, 0.2 mmol), and αꢀmethylstyrene (118 mg, 1 mmol).
Comꢀ
pound
R´
HNR2
The reaction mixture was stirred for 5 h, diluted with light
petroleum (30 mL), successively washed with water and brine,
dried over Na SO , and concentrated in vacuo. Column chroꢀ
1
3
, 2
, 4
H
Ph
HN(SiMe3)2
(R)ꢀPh(Me)CHNHSi(Ph) Bu (5)
t
2 4
2
matography of the residue on SiO (10 g) gave 264 mg (65%)
2
diethyl allylmalonate 2 as a colorless oil, R 0.44 (light petroꢀ
f
Scheme 2
1
leum—EtOAc, 9 : 1). H NMR, δ: 1.28 (t, 6 H, 2 CH , J =
3
7
7
.5 Hz); 2.62 (br.t, 2 H, CH , J = 7.2 Hz); 3.38 (t, 1 H, CH, J =
2
.2 Hz); 4.20 (q, 4 H, 2 CH O, J = 7.5 Hz); 5.00—5.20 (m, 2 H,
2
H C=); 5.67 (m, 1 H, HC=) (cf. Ref. 6).
2
(
±)ꢀDiethyl (1ꢁ3ꢀdiphenylpropꢀ2Eꢀenꢀ1ꢀyl)malonate (4) was
obtained analogously from acetate 3 with the use of amine 5
5 mol.%). The yield was 87%, a colorless oil, R 0.48 (light
(
f
1
2
0
petroleum—EtOAc, 9 : 1), [α]D 0 (с 1, СHCl ). H NMR, δ:
3
1
4
.03, 1.24 (both t, 6 H, 2 CH , J = 7.2 Hz); 4.00, 4.21 (both q,
3
H, 2 CH O, J = 7.2 Hz); 3.90—4.84 (m, 2 H, CH); 6.30—6.57
2
(
m, 2 H, HC=); 7.30 (m, 5 H, HCarom) (cf. Ref. 7).
ꢀOꢀAllyloxycarbonylꢀ1ꢁ2ꢁ5ꢁ6ꢀdiꢀOꢀisopropylideneꢀα ꢀDꢀ
glucofuranose (6). A solution of allyl chloroformate (0.53 g,
.4 mmol) was added at 0 °C for 5 min to a stirred solution
3
4
(
(
(
argon) of 1,2,5,6ꢀdiꢀOꢀisopropylideneꢀα ꢀDꢀglucofuranose
1.04 g, 4 mmol) and TMEDA (0.28 g, 2.4 mmol) in СH Cl
2
2
30 mL). The reaction mixture was stirred at 0 °C for 1 h, diluted
with СH Cl , washed with water and brine, dried over Na SO ,
2
2
2
4
and concentrated in vacuo. The residue was crystallized from
light petroleum to give compound 6 (1.21 g, 88%) as colorless
18
1
crystals, m.p. 73—75 °C, [α]D –36.9 (с 2, СHCl ). H NMR,
3
δ: 1.28, 1.32, 1.43, 1.51 (all s, 12 H, 4 CH ); 4.00—4.30 (m, 4 H);
3
4
1
1
.61 (d, 1 Н, J = 3.5 Hz); 4.68 (br.d, 2 Н, J = 5.1 Hz); 5.14 (d,
Н, J = 2.6 Hz); 5.30 (br.d, 1 H, H C=, J = 9.1 Hz); 5.30 (br.d,
2
H, H C=, J = 15.2 Hz); 5.91 (d, 1 Н, J = 3.5 Hz); 6.75—6.06
2
(
m, 1 H, HC=) (cf. Ref. 8).
Nꢀ(Phenylsulfonylacetyl)pyrrolidine (8). Hydrogen peroxide
(
30%, 5.7 mL, ~50.0 mmol) was added at 20 °С for 5 min to a
9
stirred suspension of Nꢀ(phenylthioacetyl)pyrrolidine (2.21 g,
1
0 mmol) in AcOH (15 mL). The reaction mixture was kept at
Experimental
30 °С for 1 h and at 100 °С for 20 min, cooled to 20 °С, and
diluted with water (30 mL). The product was extracted with
IR spectra were recorded on a Specord Mꢀ80 instrument.
1H and 13С NMR spectra were recorded on a Bruker ACꢀ200
CHCl . The extract was washed with water, a saturated solution
3
of NaHCO , and brine, dried over Na SO , and concentrated
3
2
4

0
Pd ꢀcatalyzed allylation of CH acids
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 11, November, 2006 2105
in vacuo. The residue was chromatographed on SiO with EtOAc
3.73 (t, 2 H, CH N, J = 6.7 Hz); 4.16 (dd, 1 H, CHS, J =
2
2
as an eluent. The yield of amide 8 was 2.41 g (95%), colorless
crystals, m.p. 119—121 °C (EtOAc). Found (%): C, 56.95;
5.4 Hz, J = 9.3 Hz); 5.05 (ddd, 1 H, H С=С, J = 1.3 Hz, J =
2
2.5 Hz, J = 10.0 Hz); 5.10 (ddd, 1 H, H С=С, J = 1.3 Hz, J =
2
H, 6.18; N, 5.55; S, 12.47. C12H15NO S. Calculated (%):
C, 56.90; H, 5.97; N, 5.53; S, 12.66. MS, m/z (Irel (%)): 190 (3),
2.5 Hz, J = 17.0 Hz); 5.64 (dddd, 1 H, HC=С, J = 6.9 Hz, J =
6.9 Hz, J = 10.0 Hz, J = 17.0 Hz); 7.50—7.95 (m, 5 H, Harom).
3
1
9
89 (24), 188 (5), 141 (7), 113 (24), 112 (100), 110 (7), 99 (7),
8 (57), 96 (23), 84 (15), 83 (54), 78 (8), 77 (52), 70 (57), 69
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 06ꢀ03ꢀ
32238).
–
1
(
14), 56 (13), 55 (36). IR (KBr), ν/cm : 629, 732, 756, 776,
8
1
60, 904—1036, 1084, 1156, 1188, 1232, 1264, 1312, 1324, 1352,
1
408, 1440, 1584, 1608, 1648, 2888—2984. H NMR, δ: 1.90
(
7
m, 4 H, 2 CH ); 3.45 (m, 4 H, 2 CH N); 3.64 (s, 2 H, CH S);
.25, 7.45 (both m, 5 H, Harom).
2
2
2
References
Nꢀ(2ꢀPhenylsulfonylpentꢀ4ꢀenoyl)pyrrolidine (9). Triphenylꢀ
phosphine (104 mg, 0.40 mmol) was added at 25 °С to a stirred
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2
3
3
THF (3 mL). After 30 min, a solution of allyl carbonate 6
(
(
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t
for 1 h, diluted with MeOBu (20 mL), and filtered through a
short pad of SiO . The filtrate was concentrated in vacuo and the
residue was chromatographed on SiO (25 g) with light petroꢀ
leum—MeOBu (1 : 1) as an eluent. The yield of amide 9 was
2
(
2
2
t
5. B. Burns, E. Merifield, M. F. Mahon, K. C. Molloy, and
50 mg (85%), m.p. 102—104 °C (EtOAc—hexane), [α]D20
0
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с 2, СHCl ). Found (%): C, 61.45; H, 6.74; N, 4.81; S, 10.90.
3
C H NO S. Calculated (%): C, 61.41; H, 6.53; N, 4.77;
1
5
19
3
+
S, 10.93. MS, m/z (Irel (%)): 293 [M] (5), 252 (3), 230 (9), 229
41), 228 (11), 200 (3), 153 (37), 152 (100), 141 (21), 136 (35),
25 (37), 124 (37), 123 (32), 112 (18), 110 (21), 104 (42), 98
(
1
(
5
9
1
2
61), 97 (24), 83 (48), 82 (29), 81 (46), 77 (51), 72 (42), 70 (88),
6 (56), 55 (72). IR (KBr), ν/cm–1: 692, 724, 772, 836, 916,
88, 1040, 1084, 1148, 1288, 1316, 1348, 1440, 1472, 1584,
1
648, 2888, 2984. H NMR, δ: 1.80—2.04 (m, 4 H, 2 CH );
2
.60—2.72 (m, 2 H, HC(3)); 3.40, 3.73 (both m, 2 H, CH N);
Received July 11, 2006
2