Palladium(II)-catalyzed intramolecular aminoacetoxylation of sugar derived alkenyl tosylsulfonamide: Total synthesis of L-deoxyallonojirimycin

Article abstract of DOI:10.1016/j.tetlet.2016.12.057

Palladium catalyzed intramolecular aminoacetoxylation of D-ribose derived alkenyl tosylsulfonamide to deliver L-deoxyallonojirimycin in an overall yield of 19%. The preliminary screening of L-deoxyallonojirimycin against carbohydrate processing enzymes showed moderate inhibitory activity against α-glucosidase (yeast) and α-mannosidases.

Full text of DOI:10.1016/j.tetlet.2016.12.057

Accepted Manuscript
Palladium(II)-Catalyzed Intramolecular Aminoacetoxylation of Sugar Derived
Alkenyl Tosylsulfonamide: Total Synthesis of L-Deoxyallonojirimycin
Pintu Das, Sama Ajay, Arun K. Shaw
PII:
S0040-4039(16)31688-4
DOI:
http://dx.doi.org/10.1016/j.tetlet.2016.12.057
TETL 48469
Reference:
Tetrahedron Letters
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Received Date:
Revised Date:
Accepted Date:
17 November 2016
14 December 2016
18 December 2016
Please cite this article as: Das, P., Ajay, S., Shaw, A.K., Palladium(II)-Catalyzed Intramolecular Aminoacetoxylation
of Sugar Derived Alkenyl Tosylsulfonamide: Total Synthesis of L-Deoxyallonojirimycin, Tetrahedron Letters
(2016), doi: http://dx.doi.org/10.1016/j.tetlet.2016.12.057
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Palladium(II)-Catalyzed Intramolecular
Aminoacetoxylation of Sugar Derived
Alkenyl Tosylsulfonamide: Total Synthesis of
L-Deoxyallonojirimycin
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Pintu Das, Sama Ajay and Arun K. Shaw

1
Tetrahedron Letters
Palladium(II)-Catalyzed Intramolecular Aminoacetoxylation of Sugar Derived
Alkenyl Tosylsulfonamide: Total Synthesis of L-Deoxyallonojirimycin
Pintu Das, Sama Ajay and Arun K. Shaw
Medicinal and Process Chemistry Division, CSIR-Central Drug Research Institute (CSIR-CDRI), Sector 10, Jankipuram Extension, Sitapur road, Lucknow-
226031, U. P., India.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Palladium catalysed intramolecular aminoacetoxylation of D-ribose derived alkenyl
tosylsulfonamide to deliver L-deoxyallonojirimycin in an overall yield of 19%. The preliminary
screening of L-deoxyallonojirimycin against carbohydrate processing enzymes showed moderate
inhibitory activity against α-glucosidase (yeast) and α-mannosidases.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Total synthesis
Deoxyallonojirimycin
Aminoacetoxylation
Mitsunobu reaction
Wittig olefination
Introduction
, and diastereoselectivity of intermolecular diamination8 of internal
alkenes with the alkene as the limiting reagent. In 2010, Wolfe and
Palladium
(II)-catalyzed
stereoselective
vicinal
co-workers developed the enantioselective synthesis of pyrrolidine
derivatives via Pd-catalyzed alkene carboamination reactions with
aryl bromides. Michael and co-workers reported a novel method
for Pd(II) catalyzed carboamination of alkenes using N-
fluorobenzenesulfonimide (NFBS) as an oxidant for the synthesis
of five-, six- and seven-membered-ring nitrogen heterocycles.9
These reports thus led to understand that the intramolecular
aminoacetoxylation of alkene (tandem C-N and C-O bond
formation) could be a method of choice for the stereoselective
construction of nitrogen heterocycles, which are common building
blocks existing in various natural products.
difunctionalization of alkene is among the most important and
powerful methodology in modern organic chemistry for the
formation
of
C-N
bond.1
Palladium-catalyzed
aminoacetoxylation2 and diamination3 of alkenes with
hypervalent iodine [PhI(O2CR)2] as the stoichiometric oxidant
has also gained much pace in the recent years. A wide variety of
nitrogen nucleophiles are known to attack the palladium (II)-
activated alkene to give an alkyl palladium (II) intermediate
followed by PhI(O2CR)2 induced oxidative cleavage of the Pd-C
bond, presumably via PdIII or PdIV intermediates. This
intermolecular difunctionalization process involves the tandem
X-N and C-X (X= N, O, C, halides, etc.) bond formation.4
As a part of our on-going programme towards synthesis of
iminosugars and azacycles using newly developed synthetic
strategies,10 we decided to investigate the synthesis of piperidine
iminosugars from sugar derived alkenyl sulphonamide by Pd(II)-
catalyzed oxidative tandem cyclization reaction. L-(+)-1-
deoxynojirimycin (2), isolated from the roots of mulberry trees11
has been shown to be inhibitor for α-glucosidases I and II12 while
1-deoxymannojirimycin (3), isolated from Lonshocarpus sericeus
by L.E. Fellows in 1979,13 exhibited a potent inhibition against α-
L-fucosidase, α-D-mannnosidase and α-D-glucosidase.14 Due to
the interesting biological activities of compounds 2 and 3, as well
as their derivatives, several stereoselective synthetic routes15 of
these types of piperidine iminosugars have been developed.
Encouraged by above literature reports, herein we disclosed
palladium catalyzed intramolecular aminoacetoxylation of sugar
derived alkene to obtain optically active L-1-deoxyallonojirimycin
1.
Figure 1. General palladium catalyzed difunctionalization.
In 2005, Sorensen5 and Muñiz6 reported the intramolecular Pd-
catalyzed aminoacetoxylation and diamination of alkenes by
trapping the Pd-C intermediate in presence of an oxidant
PhI(OAc)2.2b Later Sanford and co-workers demonstrated that
PhI(OAc)2 could serve as an oxidizing agent to facilitate C-X bond
formation by converting PdII to PdIV.7 In 2006, Liu and Stahl
reported highly regio- and diastereoselective intermolecular
aminoacetoxylation of terminal alkenes using an excess of alkene
with respect to the nitrogen nucleophile.2b Recently, Martıñez and
Muñiz modified the Stahl conditions with complete chemo-, regio-
———
 Corresponding author. Tel.: +91-9415403775, 91-7754097788; e-mail: akshaw55@yahoo.com

2
Tetrahedron
steps; (g) Pd(OAc)2, PhI(OAc)2, Bu4NOAc, DCM, 0 °C to 25 °C, 3 h,
72%.
Single step conversion of hydroxyl functionality in 6 into its
corresponding amine was performed by Mitsunobu reaction in
presence of PPh3, phthalimide and DIAD in THF at 0 °C to room
temperature. The desired phthalimido compound 11 was obtained
in 94% yield. Its conversion to the amine was done smoothly by
treating it with 40% aqueous MeNH2 at 60 °C for 3 h. The
reaction mixture was concentrated and tosyl protection of the
crude primary amine was achieved by treating it with
triethylamine and p-toluenesulfonyl chloride at 0 °C in DCM to
obtain amine 5 in overall 72% yield from 11. Its treatment with
10 mol % Pd(OAc)2 in presence of 2.0 equiv of PhI(OAc)2 and
1.0 equiv of Bu4NOAc in CH2Cl2 at 0 °C to 25 °C for 3 hours
resulted in the formation of aminoacetoxylation product 4 as an
exclusive product in 72% yield (Scheme 2).2a
Figure 2. Some piperidine iminosugars.
Results and discussion
Retrosynthetic strategy for target piperidine iminosugar 1 is
delineated in Scheme 1. We envisioned that 1 could be elaborated
from N-tosylated compound 4 which could be obtained from
alkenyl tosylsulfonamide 5 using palladium-catalyzed ring
forming aminoacetoxylation. Its synthesis could be possible
from alkenyl alcohol 6 which in turn could be accessed from
commercially available D-ribose 7 via Wittig olefination and
protecting group manipulations.
The 1D and 2D NMR experiments of compound 4 showed the
formation of piperidine skeleton but its stereochemical outcome
could not be analysed due to the appearance of overlapping
1
signals for H-5 (1H) and H-6 (2H) at 4.08-4.02 (3H) ppm in H
spectra. Therefore, in order to establish its stereochemistry
1
completely, we choose its benzyl analogue 12. In its H NMR
spectra the signals for H-5 (1H) and H-6 (2H) got separated and
appeared at 3.99-3.97 H-5 (1H) ppm and 3.57-3.53 H-6 (1H),
3.48-3.44 H-6 (1H) ppm respectively.
The structure of the product 12 was finally confirmed by
1
detailed analysis of its NMR spectral data. The H NMR spectral
Scheme 1. Retrosynthetic analysis of L-1-deoxyallonojirimycin 1.
data, combined with extensive decoupling experiments and 2D
1H-1H COSY spectra data, defined the complete connectivity of
the hydrogen atoms. NOESY correlation between H-3 and H-1,
H-3 and H-2, H-3 and H-4, H-3 and H-6 and no correlation
between H-3 and H-5 indicated that H-5 must be in equatorial
position (Figure 3). In addition, very small (1.4 Hz) coupling
constant value also supported the 1,2-di equatorial position of
proton H-4 and H-5.
Synthesis of L-1-deoxyallonojirimycin 1
Synthesis of piperidine 1, commenced from commercially
available D-ribose 7 was first converted to 2,3-O-isopropylidine-
D-ribose by treating it with 2,2-dimethoxypropane in acetone in
presence of catalytic amount of p-toluenesulfonic acid. The
primary hydroxyl group of 2,3-O-isopropylidine-D-ribose was
protected as silyl ether by using TBDMSCl and imidazole to give
the known hemiacetal 816 in 90% yield. Its Wittig methylenation
with methyltriphenylphosphonium bromide in presence of
potassium tert-butoxide in THF at 0 °C furnished alkenol 9. The
benzylation of its free hydroxyl group in DMF with BnBr and
NaH yielded compound 10. Its deprotection using
tetrabutylammonium fluoride at 0 °C afforded compound 6.
Figure 3. NOESY correlations of compound 12.
Thus, the above NMR studies established the structure of
compound 12. The stereoselective formation of 4 could be
explained by assuming that the cyclization proceeded via
transition state A in which palladium made complex with the
alkene on the α-face opposite to that of all the substituents
leading to the exclusive formation of compound 6 (Scheme 3).
Scheme 3. Transition state for the formation of 4.
Scheme 2. Reagents and conditions: (a) (i) 2,2-dimethoxypropane,
PTSA, acetone, 0 °C, 2 h, 90%; (ii) TBDMSCl, imidazole, DCM, 0 °C, 2
h, 90%; (b) Ph3PCH3Br, n-BuLi, THF, 0 °C to 25 °C, 3 h, 82%; (c)
BnBr, NaH, THF, 0 °C, 3 h, 88%; (d) TBAF, THF, 0 °C, 92%; (e) PPh3,
DIAD, phthalimide, THF, 0 °C to 20 °C to rt, overnight, 94%; (f) (i) 40%
aq. MeNH2, 60 °C, 3 h, rt.; (ii) TsCl, Et3N, DCM, 3 h, 72% over two
The conversion of the N-tosylated piperidine 4 to iminosugar
1 was completed in three-step sequence. N-detosylation of
compound 4 using several methods (Na/naphthalene, SmI2 and
Mg in methanol) turned out to be futile. Therefore, we slightly
changed our strategy at this step and thought that replacement of
more labile acetate functionality with more stable benzyl group

3
may work well as well as this modification could prevent the
need for deacetylation step at the final stage. Thus deacetylation
of compound 4 with sodium methoxide in methanol followed by
benzylation using BnBr in DMF gave compound 12 (Scheme 4).
Its N-tosyl group was deprotected by Na-napthalenide at -78 °C
within 10 min. in THF to afford compound 13 in 92% yield.17
Removal of the benzyl group and acetonide group in 13 was done
in single step by treating it with Pd(OH)2/C in the presence of H2
in methanolic HCl to obtain the target piperidine iminosugar
(2R,3R,4S,5S)-5-(hydroxymethyl)piperidine-2,3,4,-triol (1) as its
HCl salt.18
Figure 4. Michaelis-Menten plot of Activity vs Substrate
concentration for inhibition of various enzymes by piperidine 1.
The Ki were determined by non-linear regression using Graph
Pad Prism (version 6.01 for Windows, Graph Pad Software, San
Diego California USA).
Conclusions
Scheme 4. Synthesis of L-1-deoxyallonojirimycin 1: (a) (i) NaOMe,
MeOH 0 °C; (ii) BnBr, NaH, THF, 0 °C, 3 h, 88%; (b) Na-Napthalene,
THF, -78 °C, 92%; (c) H2, Pd(OH)2/C, MeOH-HCl, 12 h, 98%.
In conclusion, we have described the stereoselective synthesis
of L-1-deoxyallonojirimycin 1, started from D-ribose, with an
overall yield of 19%. The key step in the sequence is
Glycosidase Inhibition
palladium(II)-catalyzed
intramolecular
ring
forming
L-1-deoxyallonojirimycin 1 was subjected to a preliminary
screening against carbohydrate processing enzymes and its
inhibition results are summarised in Table 1. It showed moderate
inhibitory activity against α-glucosidase (yeast) and α-
mannosidase. Further efforts to obtain selective inhibitors and
their relevance to anti-cancer activity are currently underway.
aminoacetoxylation of the alkenyl sulphonamide. The title
compound was subjected to preliminary screening against
carbohydrate processing enzymes and it showed moderate
inhibitory activity against α-glucosidase (yeast) and α-
mannosidases.
Table 1. Concentration of piperidine 1 giving 50% inhibitiona (IC50)
Acknowledgments
of various glycosidases.
P.D. and S.A. thank CSIR for the award of Senior Research
Fellowship. We are thankful to Mr. A. K. Pandey for technical
assistance, and SAIF, CDRI, for providing spectral data. CSIR-
CDRI Communication No. 9347.
β-
gluco
sidase
α-
galacto
sidase
β-
galacto
sidase
α-
manno
sidase
α-L-
Fucos
idase
α-glucosidase
Asp.
nige
r
Yeast
Rice
NIc
234.76
131
References and notes
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NI
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aInhibition was competitive in all cases
bKi values are given in bold
cNI: No inhibition at 800 µM
Graphs A and B (Figure 4) represent Michaelis-Menten plot of
Activity versus substrate concentration for inhibition of various
enzymes by compound 1. The Ki values were determined by
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represented as absorbance of liberated p-nitrophenol measured at
405 nm. Competitive inhibition is indicated in each case.
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(2S,3S,4R,5R)-2-(hydroxymethyl)piperidine-3,4,5-triol
(1):
Catalytic amount of 10% Pd(OH)2/C (20 mg) was added to a solution
of 13 (40 mg, 0.104 mmol) in methanolic HCl (5 mL). A vacuum
was created in a round bottom flask containing the above reaction
mixture with the help of pump for few seconds and then the reaction
mixture was left for stirring under a positive pressure of H2 in a
balloon. After the completion of the reaction (TLC control, 48 h)
catalyst was removed by filtration, washed with methanol twice and
the combined filtrate was concentrated to afford a crude mixture
which was purified by flash column chromatography to give HCl salt
of compound 1 as a colorless oil (17 mg, 0.102 mmol, 98%). Eluent
12.
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Selected examples for the synthesis of piperidine iminosugars,
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8931-8952. (b) Cook, G. R.; Beholz, L. G.; Stille, J. R. J. Org.
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for column chromatography: Et2O/MeOH/ 25% aq. NH3 = (100/1/0,
28
v/v) to Et2O/MeOH/ 25% aq. NH3
=
(90/10/2, v/v); [α]D -25 (c
1
0.800, H2O)15d; Rf = 0.21 (2/8, MeOH/CHCl3); H NMR (400 MHz,
D2O) δ 4.20 (s, 1H), 4.04-3.85 (m, 4H), 3.37-3.28 (m, 2H), 3.15 (t, J
= 11.82 Hz, 1H); 13C NMR (100 MHz, D2O) δ 69.9, 65.3, 64.5, 57.6,
54.7, 41.5; IR (neat, cm–1) 3412, 3019, 1643, 1384; DART–HRMS:
m/z [M+H]+ Calcd for C6H14NO4 164.0922, found 164.0913.
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5
Highlights
 Completed the synthesis of L-1-
deoxyallonojirimycin, with an overall yield
of 19%.
 Palladium-catalyzed intramolecular ring
forming aminoacetoxylation is the key step.
 The
L-1-deoxyallonojirimycin
showed
moderate inhibitory activity.
 Mechanistic explanation has been given for
the key step.