Desymmetrization of meso-bicyclic hydrazines by rhodium-catalyzed enantioselective hydroformylation

Article abstract of DOI:10.1002/ejoc.200800116

An asymmetric hydroformylation of three meso-bicyclic hydrazines followed by the reduction of the formyl product afforded the corresponding desymmetrized optically enriched hydroxymethyl hydrazines (up to 77.5%ee). Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejoc.200800116

FULL PAPER
DOI: 10.1002/ejoc.200800116
Desymmetrization of meso-Bicyclic Hydrazines by Rhodium-Catalyzed
Enantioselective Hydroformylation
Chloée Bournaud,[a] Thomas Lecourt,[a] Laurent Micouin,*[a] Catherine Méliet,[b] and
Francine Agbossou-Niedercorn*[b]
Keywords: Asymmetric catalysis / Hydroformylation / Rhodium / N heterocycles
An asymmetric hydroformylation of three meso-bicyclic hy-
drazines followed by the reduction of the formyl product af-
forded the corresponding desymmetrized optically enriched
hydroxymethyl hydrazines (up to 77.5%ee).
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
Introduction
Results and Discussion
As mentioned above, we investigated the desymmetri-
zation of polycyclic hydrazines by hydroformylation with the
aim of having access to new valuable intermediates for fur-
ther elaboration into polyfunctional cyclopentanes. Initial
experiments were carried out on substrate S1 (Figure 1).
The structural analogy between this compound and nor-
bornene prompted us to first evaluate reaction conditions
described by Stille for norbornene hydroformylation.[5c]
However, no hydroformylated product could be obtained in
the presence of a platinum catalyst generated from Pt(cod)-
Cl2 (1 mol-%), SnCl2 (2 mol-%) and (S,S)-bppm (2 mol-%)
(Figure 2) under the following conditions: syngas (CO/H2,
1:1) 60 bar, 60 °C, 18 h. The lower initial pressure applied
relative to that utilized by Stille for the hydroformylation of
norbornene (165 bar) can account for this result. As
we planned to apply rather mild reaction conditions
(Ͻ100 bar), we favoured the use of rhodium-based catalytic
systems.[1] The next attempt at hydroformylation of S1 was
performed in the presence of the catalytic system obtained
from Rh(acac)(CO)2 and (S,S)-bppm (1:4) in toluene at
80 °C under 40 bar of syngas (Scheme 1).
The enantioselective transition-metal-catalyzed hydro-
formylation of olefins constitutes one of the most attractive
atom economic, clean and environmentally friendly process
for introduction of a formyl residue with a concomitant cre-
ation of chirality in an organic compound.[1,2] In this con-
text, a lot of effort has been devoted to the design of phos-
phorus-based chiral ligands in order to modify platinum
and rhodium hydroformylation catalysts.[1–4] From a sub-
strate standpoint, styrene and other vinyl arenes, vinyl ace-
tates and allyl cyanides, for example,[3,4] have been used in
order to evaluate the newly designed catalytic systems. Con-
versely, norbornene and its related derivatives have been hy-
droformylated selectively into the exo-formyl products in
the presence of platinum and rhodium catalysts modified
by chiral diphosphorous auxiliaries.[5,6]
We have an ongoing interest both in asymmetric trans-
formations involving bicyclic hydrazines to synthesize
polyfunctional aminocyclopentanes[7–9] and hydrofor-
mylation.[10] As such, we reported recently on the re-
arrangement,[11,12] hydroboration[8,13,14] and asymmetric
nucleophilic ring opening[15,16] of bicyclohydrazine deriva-
tives. We extended our study on such substrates and ex-
plored their behaviour under enantioselective hydrofor-
mylation conditions. Here, we report on the desymmetri-
zation though asymmetric hydroformylation of three bi-
cyclic hydrazine substrates.
Figure 1. Substrates for hydroformylation studies.
[a] Université Paris Descartes, Laboratoire de Chimie Thérapeu-
tique UMR 8638
The conversion was quantitative as determined by 1H
NMR spectroscopy, and hydroformylated product 2 was
isolated in 84% yield after workup as a single exo dia-
stereomer. No hydrogenated derivative could be detected in
the crude reaction mixture. As the determination of optical
purity could not be carried out on aldehyde 2, because of
4 avenue de l’Observatoire
75270 Paris Cedex 06, France
E-mail: laurent.micouin@univ-paris5.fr
[b] Université des Sciences et Technologies de Lille, Unité de Cata-
lyse et de Chimie du Solide UMR 8181, ENSCL (CHIMIE)
Bât C7 B. P. 90108, 59652 Villeneuve d’Ascq Cedex, France
E-mail: francine.agbossou@ensc-lille.fr
2298
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2008, 2298–2302

Desymmetrization of meso-Bicyclic Hydrazines
subjected to oxidative cleavage, leading to hydroxy silyl de-
rivative 5 in 95% overall yield (Scheme 2).[17] Then, de-
silylation provided primary alcohol ent-3 in 87% isolated
yield and with 80%ee determined by HPLC. Because the
absolute configuration of hydroboration product 6 resulting
from the transformation of S1 under the same catalytic con-
ditions followed by an oxidative cleavage had previously
been established to be (1S,4R,5R), a (1R,4R,5R) configura-
tion could be assigned to alcohol ent-3. As the retention
times for the major isomers obtained following both syn-
thetic routes depicted in Schemes 1 and 2 were complemen-
tary, we deduced that alcohol 3 possess the (1S,4S,5S) abso-
lute configuration.
Figure 2. Chiral ligands used in this study.
Scheme 1. Hydroformylation of S1.
its partial chemical and configurational instability, the
crude was first reduced into corresponding alcohol 3
(NaBH4, MeOH, 0 °C, 80%) prior to the determination of
enantiomeric purity by chiral HPLC. An encouraging
44%ee was obtained.
The absolute configuration of the major enantiomer was
assessed by a chemical correlation. Thus, we first performed
an enantioselective hydroboration of substrate S1 followed
by the trapping of hydroborated intermediate 4 by trimeth-
Scheme 2. Chemical correlation for the assignment of the absolute
ylsilyldiazomethane. The homologated boronate was then configuration of 3.
Table 1. Asymmetric hydroformylation of S1.[a]
Entry Rh source
Chiral auxiliary
Rh/ligand
PH /CO [bar]
T [°C]
Yield of 3 [%][b] ee of alcohol [%][c]
2
1
2
3
4
5
6
7
8
Rh(acac)(CO)2
(S,S)-bppm
(S,S)-bppm
(S,S)-bppm
(S,S)-bppm
(S,S)-bppm
(S,S)-bppm
1:4
1:3
1:2
1:1.2
1:2
1:2
1:2
1:2
1:2
1:2
1:2
1:4
1:2
1:4
40
40
40
40
20
20
20
45
45
45
20
45
30
30
80
80
80
80
45
45
45
80
60
45
20
80
60
50
88
87
84
85
85
18
88
84
84
85
80
72
84
86
44
46
45
37
53
50
53
45
49
53
59
13
53
32
Rh(acac)(CO)2
Rh(acac)(CO)2
Rh(acac)(CO)2
Rh(acac)(CO)2
[Rh(cod)Cl]2
Rh(H)CO(PPh3)3 (S,S)-bppm
Rh(acac)(CO)2
Rh(acac)(CO)2
Rh(acac)(CO)2
Rh(acac)(CO)2
Rh(acac)(CO)2
Rh(acac)(CO)2
Rh(acac)(CO)2
(S,S)-bppm
(S,S)-bppm
(S,S)-bppm
(S,S)-bppm
(R,R)-bdpp
(S,S,R,R)-tangphos
(R,S)-binaphos
9
10
11
12
13
14[d]
[a] General conditions for hydroformylation: Rh precursor (1 mol-%), toluene (5 mL), unoptimized reaction times of 15 or 18 h. [b] The
conversion of S1 is total in all cases. Yield of isolated product 3 obtained by reduction of 2. [c] Determination of ee was carried out on
the alcohol by chiral HPLC, configuration of the major enantiomer (1S,4S,5S), see text. [d] Reaction time of 4 h.
Eur. J. Org. Chem. 2008, 2298–2302
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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C. Bournaud, T. Lecourt, L. Micouin, C. Méliet, F. Agbossou-Niedercorn
FULL PAPER
Table 2. Asymmetric hydroformylation of S1–S3.[a]
Entry Substrate L*
PH /CO [bar]
T [°C]
Time [h]
Conv. [%][b] Yield [%][c]
ee [%][d]
2
1
2
3
4
5
6
7
8
S1
S1
S1
S1
S1
S1
S2
S2
S2
S2
S2
S3
S3
(S,S)-bppm
(S,S)-bppm
(S,S)-bppm
(S,S)-bppm
(S,S,R,R)-tangphos
(S,S,R,R)-tangphos
(S,S)-bppm
(S,S)-bppm
(S,S)-bppm
40
20
20
100
30
100
45
20
100
30
95
45
80
45
20
–4
60
–4
80
45
–4
60
–6
20
–4
18
15
24
16
15
20
15
15
20
15
20
15
20
100
100
100
100
100
100
100
100
40
84
85
80
74
84
90
84
90
22
80
33
42
21
45
53
59
59
53
34
52[e]
49[e]
23[e]
29[e]
7[e]
9
10
11
12
13
(S,S,R,R)-tangphos
(S,S,R,R)-tangphos
(S,S)-bppm
100
nd
nd
42[e]
77.5[e]
(S,S)-bppm
100
30
[a] General conditions of hydroformylation: Rh(acac)(CO)2 (1 mol-%), chiral auxiliary (2 mol-%), toluene (5 mL). [b] Conversion of S1–
1
S3 determined by H NMR spectroscopy. [c] Yield of the isolated reduction products. [d] Determination of ee was carried out on the
alcohol by chiral HPLC, configuration of the major enantiomer (1S,4S,5S), see text. [e] Absolute configuration not determined.
The variation of the hydroformylation parameters (li- Nevertheless, this substrate led to the best result in terms
gand/Rh ratio, source of Rh, temperature, pressure, ligand) of selectivity as, after reduction, the corresponding alcohol
on the reaction course were then investigated (Table 1). A could be isolated with 77.5%ee. It appears thus that the
rhodium/ligand ratio from 1:1.2 to 1:4 delivered close desymmetrization of meso-hydrazines with the use of cata-
catalytic results, especially in terms of enantioselectivity lytic asymmetric hydroformylation reactions is far from be-
(Table 1, Entries 1–4). Two rhodium sources [Rh(acac)- ing straightforward and highly substrate dependent.
(CO)2 and Rh(H)(CO)(PPh3)3] generated catalysts of sim-
ilar efficiencies, whereas [Rh(cod)Cl]2 proved to be less ef-
ficient for this transformation (Table 1, Entries 5–7). The
temperature had a significant impact on the selectivity: the
highest ee was reached at 20 °C (59%ee at 20 °C vs. 45%ee
at 80 °C; Table 1, Entries 8–11). Among the four chiral li-
gands evaluated, (S,S)-bppm proved to be the most ef-
ficient, as 59%ee was obtained at 20 °C. In our hands, the
use of the (S,S,R,R)-tangphos ligand at 60 °C led to the
hydroformylated compound with a 53%ee, whereas a
60%ee was reported for this reaction conducted at room
Scheme 3. Hydroformylation of substrates S1–S3.
temperature by Huang et al. during our investigations.[6]
The use of (S,S)-bdpp and (R,S)-binaphos provided selec-
tivities of 13% and 32%ee, respectively (Table 1, En-
tries 11–14).
Conclusions
From analysis of the results obtained with substrate S1
We showed that a desymmetrization of meso-bicyclic hy-
drazines is possible through asymmetric hydroformylation.
The reaction proceeds efficiently with a high diastereoselec-
tivity as the exo products are obtained exclusively. The
alcohols prepared by the reduction of the hydroformylated
products could be obtained with an ee up to 77.5% under
the catalytic conditions examined in this study. This reac-
tion seems to be much more substrate dependent than hy-
droboration, and its optimization is still a challenging task.
while varying the catalytic parameters, we selected the
(S,S)-bppm and (S,S,R,R)-tangphos ligands to examine the
hydroformylation of two other bicyclic hydrazine substrates
S2 and S3 into P2 and P3 after reduction of the intermedi-
ate formyl derivatives (Figure 1 and Scheme 3). The results
are summarized in Table 2. Despite their apparent struc-
tural similarities, the three substrates proved to behave dif-
ferently in the hydroformylation reaction. Thus, lowering
the reaction temperature led to an improvement in the
enantioselectivity when working on substrate S1 (Table 2,
Entries 1–4) and S3 (Table 2, Entries 12, 13) with the bppm
ligand, whereas it proved to be detrimental for both catalyst
rate and selectivity for substrate S2 (Table 2, Entries 7–9).
A similar behaviour could be observed with the (S,S,R,R)-
tangphos ligand for substrates S1 and S2 (Table 2, En-
tries 5,6 and 10, 11). Substrate S3 was not very soluble in
the reaction medium. Thus, the yield of the aldehyde was
Experimental Section
1H NMR and 13C NMR spectra were recorded with a Bruker
Avance 400 or 300 spectrometer at 25 °C. Chemical shifts are re-
ported in ppm downfield of internal tetramethylsilane. All melting
points are uncorrected. All reagents are commercially available and
were used without further purification. The organic syntheses were
lower than that for the two other substrates, S1 and S2. carried out under classical conditions unless otherwise stated. The
2300 Eur. J. Org. Chem. 2008, 2298–2302
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Desymmetrization of meso-Bicyclic Hydrazines
reactions were performed under an atmosphere of nitrogen. THF
was dried with CaCl2, filtered through basic alumina, and distilled
from Na under an atmosphere of nitrogen. Toluene was distilled
from Na under an atmosphere of nitrogen. Substrates S1–S3 were
prepared following reported procedures.[15]
220 nm, flow = 0.8 mLmin–1; eluent = hexane/iPrOH, 70:30): tR1
= 11.9 min, tR2 = 13.8 min.
2-(Hydroxymethyl)-1,4-methano-1,2,3,4-tetrahydropyridazino-
[1,2-b]phthalazine-6,11-dione (P3): Yellow oil (125 mg, 42%). 1H
NMR (400 MHz, CDCl3): δ = 1.66 (m, 1 H), 2.08 (s, 2 H), 2.15
(m, 1 H), 2.45 (m, 1 H), 3.53 (m, 1 H), 3.69 (br. s, 1 H), 3.75 (m,
1 H), 5.37 (br. s, 1 H), 5.43 (br. s, 1 H), 7.76 (m, 2 H), 8.26 (m, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 31.8, 35.4, 43.7, 58.6,
60.4, 63.9, 127.3, 129.9, 133.1, 153.4, 153.7 ppm. MS (ES): m/z =
281 [M + Na]+. HPLC (concentration = 0.1 gL–1 in a 20-mL injec-
tion loop; Chiralpack AD column, 0.46 cm I.D. ϫ 25 cm, equipped
with a precolumn, 0.46 cm I. D. ϫ 5 cm; λ = 220 nm; flow =
0.8 mLmin–1; eluent = hexane/iPrOH, 80:20): tR1 = 14.18 min, tR2
= 15.56 min.
General Procedure for Hydroformylation: Under an atmosphere of
nitrogen, a Schlenk flask was charged with a magnetic stir bar,
Rh(acac)(CO)2 (2.6 mg, 0.01 mmol), the chiral auxiliary
(0.02 mmol), and toluene (5 mL). The solution was stirred at room
temperature for 1 h. The substrate (1 mmol) was placed in a
double-walled stainless steel autoclave equipped with a stir bar un-
der an atmosphere of nitrogen. The solution containing the rho-
dium precatalyst was transferred into the autoclave by cannula un-
der an atmosphere of nitrogen. The autoclave was then pressurized
with syngas (CO/H2, 1:1) at the selected pressure and placed at the
desired temperature. At the end of the reaction, the autoclave was
cooled to room temperature and depressurized. Toluene was evapo-
rated under reduced pressure. The crude residue was dissolved in
methanol, and the mixture was cooled to 0 °C. NaBH4 (113 mg,
3 mmol) was added in small portions over 30 min. Then, ethyl ace-
tate (30 mL) and saturated ammonium chloride (10 mL) were
added. The aqueous phase was extracted with ethyl acetate
(2ϫ30 mL). The combined organic layers were washed with brine
(20 mL) and dried with magnesium sulfate. After filtration and
evaporation of the solvent, the crude residue was purified through
silica gel flash chromatography.
Chemical Correlation: [Rh(cod)Cl]2 (5 mg, 0.01 mmol), (S,S)-bdpp
(8.8 mg, 0.02 mmol), and S1 (365 mg, 1 mmol) were placed in a
Schlenk tube, dried under vacuum (0.1 Torr) for 1 h, and then
placed under an atmosphere of argon. DME (4 mL) was degassed
at –50 °C and added to the mixture at this temperature. The yellow-
green slurry was stirred at –50 °C for 30 min. Catecholborane
(210 µL, 2 mmol) was then added dropwise, and the mixture be-
came orange but remained heterogeneous. The reaction was kept
at –50 °C for an additional 30 min. The solvent and the excess
amount of reagent were then carefully removed under vacuum
(0.1 Torr, 3 h) to give intermediate borane 4 as a dark-yellow foam.
A solution of 4 in THF (6 mL) under an atmosphere of argon was
then added over a 2- solution of trimethylsilyldiazomethane in
Et2O (2.5 mL, 5 mmol). After heating at reflux overnight, freshly
prepared mixture of 2  aqueous sodium hydroxide and 30% hy-
drogen peroxide (1:1, 10 mL) were then added dropwise at 0 °C,
which turned the solution to black. The mixture was stirred for an
additional 4 h at room temperature. After extraction with EtOAc
(3ϫ20 mL), the combined organic layers was washed with 1  HCl
(20 mL), dried with MgSO4, filtered, and concentrated. The crude
reaction mixture was then purified by silica gel flash chromatog-
raphy (cyclohexane/ethyl acetate, 2:1) to give 5 as a mixture of dia-
stereomers (446 mg, 95%). Tetrabutylammonium fluoride (250 mg,
0.8 mmol) was added to a solution of 5 (188 mg, 0.4 mmol) in THF
(2 mL) and stirred at room temperature for 24 h. More reagent was
then added (250 mg, 0.8 mmol), and the mixture was kept at room
temperature until complete consumption of the starting material.
After concentration under vacuum, the crude reaction mixture was
purified by silica gel flash chromatography to give 3 (138 mg, 87%).
The absolute configuration of compound 3 was established from
the known configuration of compound 6, obtained by an oxidative
treatment of boronate 5.[7]
Dibenzyl 5-Formyl-2,3-diazabicyclo[2.2.1]heptane-2,3-dicarboxylate
(2): Yellow oil (330 mg, 84%). 1H NMR (400 MHz, CDCl3): δ =
1.46 (d, J = 10.5 Hz, 1 H), 1.69 (d, J = 10.5 Hz, 1 H), 1.81–2.20
(m, 2 H), 2.99 (br. s, 1 H), 4.51–5.15 (m, 2 H), 5.10–5.27 (m, 4 H),
7.26–7.34 (m, 10 H), 9.46 (br. s, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 29.3, 36.2, 52.3, 60.5, 68.3, 128.1, 128.4, 128.7, 135.9,
157.2, 199.1 ppm.
Dibenzyl 5-(Hydroxymethyl)-2,3-diazabicyclo[2.2.1]heptane-2,3-di-
carboxylate (3, P1): Yellow oil (364 mg, 80%). 1H NMR (400 MHz,
CDCl3): δ = 1.00–1.30 (m, 1 H), 1.50–1.70 (m, 2 H), 1.80–2.00 (m,
1 H), 2.10–2.40 (m, 2 H), 3.20–3.40 (m, 1 H), 3.40–3.60 (br. s, 1
H), 4.40–4.80 (m, 2 H), 5.10–5.30 (m, 4 H), 7.26–7.32 (m, 10 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 32.5, 35.3, 42.7, 60.5, 62.1,
64.2, 68.1, 128.1, 128.3, 128.6, 136.1, 157.7 ppm. HRMS: calcd.
for C22H25N2O5 397.1763; found 397.1765. HPLC (concentration
= 0.1 gL–1 in a 20-mL injection loop; Chiralpack AD column,
0.46 cm I.D. ϫ 25 cm, equipped with a precolumn, 0.46 cm I. D.
ϫ 5 cm; λ = 220 nm; flow = 0.8 mLmin–1; eluent = hexane/iPrOH,
70:30): tR1 = 11.87 min, tR2 = 13.81 min.
3,5-Dioxo-4-phenyl-2,4,6-triazatricyclo[5.2.1.02,6]decane-8-carbal-
dehyde: White amorphous solid (270 mg, 99 %). 1H NMR
(300 MHz, CDCl3): δ = 1.70 (d, J = 11.0 Hz, 1 H), 1.91 (d, J =
11.0 Hz, 1 H), 2.15 (dd, J = 11.5, 9.0 Hz, 1 H), 2.29 (m, 1 H), 3.26
(m, 1 H), 4.99 (s, 1 H), 5.31 (s, 1 H), 7.40 (m, 1 H), 7.47 (m, 4 H),
9.78 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 28.7, 36.9,
52.4, 60.1, 125.5, 128.6, 129.4, 131.4, 157.0, 198.2 ppm.
8-(Hydroxymethyl)-4-phenyl-2,4,6-triazatricyclo[5.2.1.02,6]decane-
3,5-dione (P2): White solid (245 mg, 90%). M.p. 180–182 °C. 1H
NMR (300 MHz, CDCl3): δ = 1.47 (ddd, J = 13.0, 5.0, 3.0 Hz, 1
H), 1.94 (m, 2 H), 2.11 (m, 2 H), 2.41 (m, 1 H), 3.44 (m, 1 H), 3.64
(m, 1 H), 4.68 (br. s, 1 H), 4.88 (br. s, 1 H), 7.40 (m, 1 H), 7.47 (m,
2 H), 7.49 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 31.5,
36.2, 43.0, 60.3, 61.9, 63.7, 125.6, 128.5, 129.3, 131.6, 157.0 ppm.
MS (ES): m/z = 296 [M + Na]+. HPLC (concentration: 0.1 gL–1 in
a 20-mL injection loop; Chiralpack AD column. 0.46 cm I.D. ϫ
25 cm, equipped with a precolumn, 0.46 cm I. D. ϫ 5 cm; λ =
Acknowledgments
We thank Pr. Kyoko Nozaki for a generous gift of binaphos. We
thank the “Centre National de la Recherche Scientifique” and the
“Ministère de la Recherche et de l’Enseignement Supérieur” (grant
to C. B.) for financial support.
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C. Bournaud, T. Lecourt, L. Micouin, C. Méliet, F. Agbossou-Niedercorn
FULL PAPER
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Received: January 30, 2008
Published Online: March 20, 2008
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