Aminohydroxylation of divinylcarbinol and its application to the synthesis of bicyclic hydroxypyrrolidine and aminotetrahydrofuran building blocks

Article abstract of DOI:10.2478/s11696-012-0224-5

Aminohydroxylation of prochiral divinylcarbinol and subsequent Pd(II)-catalysed oxy-/amidocarbonylation of aminopentenediols is reported. The method was applied to the preparation of useful building blocks for syntheses of cytotoxic jaspines and glycosidase inhibitor DLX-homologues. The key intermediates, tetrahydrofuranolactones (l-arabino-II) and pyrrolidinolactones (l-arabino-IX and l-xylo-IX), were prepared in a short 2-step sequence from divinylcarbinol.

Full text of DOI:10.2478/s11696-012-0224-5

Chemical Papers 67 (1) 66–75 (2013)
DOI: 10.2478/s11696-012-0224-5
ORIGINAL PAPER
Aminohydroxylation of divinylcarbinol and its application
to the synthesis of bicyclic hydroxypyrrolidine
and aminotetrahydrofuran building blocks
a
b
a
aOľga Caletková, Diana Ďurišová, Naďa Prónayová, Tibor Gracza*
aDepartment of Organic Chemistry, bCentral NMR Laboratories, Faculty of Chemical and Food Technology, Slovak University
of Technology, Radlinského 9, 812 37 Bratislava, Slovakia
Received 30 March 2012; Revised 21 May 2012; Accepted 25 May 2012
Dedicated to Professor Štefan Toma on the occasion of his 75th birthday
Aminohydroxylation of prochiral divinylcarbinol and subsequent Pd(II)-catalysed oxy-/amido-
carbonylation of aminopentenediols is reported. The method was applied to the preparation of useful
building blocks for syntheses of cytotoxic jaspines and glycosidase inhibitor DLX-homologues. The
key intermediates, tetrahydrofuranolactones (l-arabino-II) and pyrrolidinolactones (l-arabino-IX
and l-xylo-IX), were prepared in a short 2-step sequence from divinylcarbinol.
c
ꢀ 2012 Institute of Chemistry, Slovak Academy of Sciences
Keywords: Sharpless aminohydroxylation, Pd(II)-catalysed oxy-/amidocarbonylation, jaspine B,
pachastrissamine, DLX-homologues
Introduction
the articles cited in their review). The biological ac-
tivities of numerous synthetic analogues and epimers
have also been prepared and tested.
Pachastrissamine (jaspine B, I ) (Fig. 1), the first
naturally occurring anhydrophytosphingosine deriva-
tive, is a metabolite isolated from the Okinawa marine
sponge Pachastrissa sp. (Kuroda et al., 2002). The
Debitus research group reported isolation of the same
natural product from a different marine sponge Jaspis
sp. (Ledroit et al., 2003). In anti-cancer assays, this
novel sphingosine derivative proved to be the most
potent compound against the A549 human lung car-
cinoma cell line isolated from the Jaspis genus. The
combination of potent biological properties and rela-
tively straightforward molecular structures has led to
the development of a number of its synthetic prepa-
rations (Llaveria et al., 2011; Passiniemi & Koski-
nen, 2011; Yoshimitsu et al., 2011; Srinivas Rao &
Venkateswara Rao, 2011; Urano et al., 2010; Salma et
al., 2010; Inuki et al., 2009, 2010; Yoshimitsu et al.,
2010; Vichare & Chattopadhyay, 2010; Canals et al.,
2009; Enders et al., 2008; Abraham et al., 2008, and
Previous investigations in our laboratory have
demonstrated that the Pd(II)-catalysed oxy- and ami-
docarbonylation of unsaturated polyols and amino
polyols represent an efficient entry to cis-fused 5-
membered bicyclic lactones (Gracza et al., 1991;
Jäger et al., 1997; Hu¨mmer et al., 1997). This
methodology has been used as the key step in a
number of natural product syntheses (Gracza &
Jäger, 1992, 1994; Dixon et al., 1999; Babjak et
al., 2002, 2005; Karlubíková et al., 2011). Here we
report on a further application of this versatile
methodology to encompass the asymmetric syntheses
of the 3,6-anhydro-2,5-dideoxy-5-R-amino-l-arabino-
1,4-hexonolactones (l-arabino-IIa, l-arabino-IIb, N-
R-2,3,6-trideoxy-3,6-imino-l-arabino-1,4-hexonolacto-
nes (l-arabino-IXa, l-arabino-IXb), and N-R-2,3,6-
trideoxy-3,6-imino-l-xylo-1,4-hexonolactones (l-xylo-
IXa, l-xylo-IXb).
*Corresponding author, e-mail: tibor.gracza@stuba.sk

O. Caletková et al./Chemical Papers 67 (1) 66–75 (2013)
67
Fig. 1. Retrosynthetic analysis of pachastrissamine (jaspine B) (I). Reaction conditions: i) multi-step procedure described by
Bhaket et al. (2005).
Experimental
the addition of a saturated sodium metabisulphite so-
lution (20 mL) at 0◦C and stirred for 15 min. The
two phases were separated and the aqueous phase was
extracted with EtOAc (3 × 15 mL). The combined or-
ganic phases were washed with water (20 mL), brine
(50 mL), dried with MgSO4, pre-concentrated, and
purified by flash chromatography.
Commercial reagents were used without further
purification. All solvents were distilled before use.
Hexanes refer to the fraction boiling at 60–65◦C. Flash
column liquid chromatography (FLC) was performed
on silica gel Kieselgel 60 (40–63 µm, 230–400 mesh)
using a Buchi Sepacoreꢀ preparative MPLC system
and analytical thin-layer chromatography (TLC) was
performed on aluminium plates pre-coated with either
0.2 mm (DC-Alufolien, Merck) or 0.25 mm silica gel 60
F254 (ALUGRAMꢀ SIL G/UV254, Macherey-Nagel).
The compounds were visualised by UV fluorescence
and by dipping the plates in an aqueous H2SO4 so-
lution of cerium sulphate/ammonium molybdate fol-
lowed by charring with a heat-gun. Melting points
were determined on a Bu¨chi B-540 apparatus and are
uncorrected. Optical rotations were measured with a
JASCO P-2000 polarimeter. FTIR spectra were ob-
tained on a Nicolet 5700 spectrometer (Thermo Elec-
tron) equipped with a Smart Orbit (diamond crys-
tal ATR) accessory, using the reflectance technique
(4000–400 cm−1). Mass spectra (MS) were measured
on an Agilent 1260B LCMS system. An MS detector
was assembled with a multimode ion source (ESI +
APCI) in positive mode, 50 % scan and 50 % SIM.
1H (300 MHz or 600 MHz) and 13C NMR (75 MHz
or 150 MHz) spectra were recorded on either Mer-
curyPlus or Unity Inova spectrometers (Varian, USA),
respectively. Chemical shifts are referenced to the
tetramethylsilane (TMS) as internal standard or to
the solvent residual peak (13C NMR). Compounds are
numbered according to the IUPAC nomenclature.
General procedure for aminohydroxylation
with chloramine T
Chloramine T was dissolved in a mixture of n-
PrOH (8 mL) and water (15 mL). The ligand was
added followed by the same procedure as for aminohy-
droxylation with benzyl carbamate (Reddy & Sharp-
less, 1998).
General procedure for desilylation
Aminoalcohol was dissolved in MeOH (10 mL
per mmol of substrate) and Dowexꢀ 50W X8 (1 g
per mmol of substrate) was added. The reaction
mixture was stirred at ambient temperature until
completed (overnight). Ionex was removed by filtra-
tion, washed with MeOH, and the solution was pre-
concentrated. The unprotected product was used in
cyclisation without further purification.
General procedure for Pd(II)-catalysed cycli-
sation
A 25 mL flask equipped with a side inlet with a
stopcock was filled with AcONa (anhydrous, 3 eq),
CuCl2 (anhydrous, 3 eq), and PdCl2 (0.1 eq). The
flask was evacuated, filled with CO via balloon and
the solution of a substrate (1.0 eq) in glacial AcOH
(10 mL per mmol of substrate) was added. The mix-
ture was vigorously stirred at ambient temperature
in the CO atmosphere (balloon) overnight until the
mixture changed colour from green to pale brown.
The reaction mixture was diluted with EtOAc, filtered
through Celite, and pre-concentrated. Purification by
flash chromatography on a column of silica gel afforded
the appropriate compound.
General procedure for aminohydroxylation
with benzyl carbamate
A freshly prepared aqueous solution of NaOH
(96 mg, 2.4 mmol) in water (15 mL) was added
to a stirred solution of benzyl carbamate (363 mg,
2.4 mmol) in propan-1-ol (n-PrOH) (8 mL), followed
by the addition of tert-butyl hypochlorite (t-BuOCl)
(261 mg, 2.4 mmol). After 5 min, a solution of lig-
and (0.1 mmol) in n-PrOH (7 mL) was added, fol-
lowed by the addition of a substrate (2.0 mmol) dis-
solved in n-PrOH (10 mL) and K2OsO2(OH)4 (30 mg,
0.08 mmol). This mixture was stirred at ambient tem-
perature for 24 h, then the reaction was quenched by
Results and discussion
In the course of our long-term programme directed

68
O. Caletková et al./Chemical Papers 67 (1) 66–75 (2013)
Fig. 2. Aminohydroxylation of IV and VII. Reaction conditions: i) K2OsO4 · 2H2O, ligand, R1NH2, aq. NaOH, t-BuOCl, solvent,
ambient temperature.
influence of the N-protecting groups of chloramines,
ligands and solvent on the yield of aminodiols III, V,
VI, VIII, as well as the selectivity of the reaction. The
results are summarised in Tables 1 and 2.
Both substrates, the unprotected DVC (IV ) and
the O-tert-butyldimethylsilyl-protected DVC (VII ),
were found to participate efficiently in the asymmetric
aminohydroxylation providing corresponding amin-
odiols III, V, VI, and VIII with anti-diastereoselecti-
vity as expected for a matched case (entries 1–13). Ac-
cording to the aminohydroxylation of allylic alcohols
towards the application of Pd-catalysed cyclisation
of unsaturated polyols to natural product synthe-
sis, we decided to apply domino intramolecular Pd-
cyclisation/carbonylation as the key step in the syn-
thesis of jaspine B. Our retrosynthetic plan (Fig. 1)
called for enantioselective preparation of the (2S,3R)-
2-N-R1-aminopent-4-ene-1,3-diol (anti-III ) as the key
substrate, which is accessible from divinylcarbinol IV
employing the Sharpless asymmetric aminohydroxyla-
tion as the source of chirality. For the second key step,
being oxycarbonylating bicyclisation of anti-III, we
took advantage of recent progress in Pd(II)-catalysed
carbonylation of unsaturated polyols, which turned
out bicyclic lactones with excellent 1,5-threo selectiv-
ity (Gracza et al., 1991; Jäger et al., 1997; Gracza &
Jäger, 1992, 1994; Dixon et al., 1999; Babjak et al.,
2002, 2005).
The study directed towards the synthesis of the
lactone l-arabino-II started with aminohydroxylation
of divinylcarbinol (DVC). DVC, with two potentially
reactive enantiotopic vinyl groups, represents a distin-
guished substrate for asymmetric functionalisation of
a double bond. The Sharpless asymmetric epoxidation
of this substrate is well established and has been used
successfully in a number of total syntheses of natural
products (selected papers: e.g. Schreiber et al., 1987;
Häfele et al., 1986; Jäger & Hu¨mmer, 1990; Nicolaou
et al., 1998; Romero & Wong, 2000; Singh & Guiry,
2009; Wang et al., 2009; Crimmins et al., 2009). Sim-
ilarly, asymmetric dihydroxylation of protected DVC,
pent-1,4-dien-3-yl 4-methoxybenzoate was described
with high enantiomeric and diastereomeric excesses
(Corey et al., 1995). To the best of our knowledge,
the Sharpless asymmetric aminohydroxylation of this
unique substrate has not been yet published; however,
potential products prepared in this manner constitute
interesting chirons for the synthesis of heterocyclic
skeletons. Hence, we decided to explore the aminohy-
droxylation of DVC (IV ) and tert-butyldimethylsilyl
ether (VII ) (Fig. 2). Aminohydroxylation of IV was
initially carried out using the first generation of the
aminohydroxylation reagent reported by Sharpless (Li
et al., 1996), i.e. using chloramine T (TsNClNa) as
an oxidant nitrogen source. Next, we scrutinised the
(Angelaud et al., 1997) using (DHQD)
2Phal-ligand
(entries 1, 3, 5, 6, 8, 10, 12), the predominant forma-
tion of regioisomers V and VIII with an amido moiety
attached to the terminal carbon was observed. In or-
der to reverse the regioselectivity of the reaction, we
performed the reaction employing (DHQD)2AQN as a
chiral ligand. Unfortunately, in contrast to the amino-
hydroxylation of cinnamates (Tao et al., 1998), replac-
ing Phal-core with an anthraquinone (AQN) core of
cinchona ligands did not cause a dramatic reversal of
the regioselectivity (entries 2, 4, 7, 9, 11, 13). From the
results summarised in Table 2, it is clear that neither
the change in the ligand structure nor the character
of N-source and the solvent had a significant influence
on the regio- or diastereoselective outcome of the reac-
tion. Aminohydroxylation of IV using either benzyl-
carbamate or sulphonamide afforded an inseparable
mixture of products (regio- and diastereomers). In-
troducing a bulky TBS-protecting group into VII did
not significantly increase diastereoselectivity of the re-
action; however the silylated aminopentenediols anti-
VIII, syn-VIII, and anti-VI could be readily separated
by flash chromatography.
With the separated aminodiols anti-VIII, syn-VIII,
and anti-VI prepared, the following synthesis was con-
ducted in parallel. Firstly, the silyl-protecting group
was removed by acidic hydrolysis with Dowex H+
in methanol and the unprotected aminodiols anti-
V, syn-V, and anti-III were subjected to the second
crucial step of the syntheses. The domino Pd(II)-
cyclisation/oxycarbonylation reaction was carried out
under standard reaction conditions (Gracza et al.,
1991; Hu¨mmer et al., 1997) affording bicyclic lac-

O. Caletková et al./Chemical Papers 67 (1) 66–75 (2013)
Table 1. Physical and spectral data of newly prepared compounds
69
Compound
Physical and spectral data
syn-VIIIa
Yield = 7 % (from VII); [α]2D0 = –0.5◦ (c = 1.122, CHCl3)
FTIR, ν˜/cm−1: 3419, 3350, 3066, 3034, 2952, 2927, 2856, 1700, 1518, 1471, 1462, 1251, 1080, 835, 776, 696
1H NMR (300 MHz, CDCl3), δ: 0.05, 0.07 (2s, 2 × 3H, Si(CH3)2), 0.90 (s, 9H, C(CH3)3), 2.72 (bs, 1H,
OH), 3.13 (ddd, 1H, J = 5.1 Hz, J = 7.8 Hz, J1A,1B = 13.2 Hz, H-1A), 3.41 (ddd, 1H, J = 3.3 Hz, J =
6.4 Hz, J1A,1B = 13.3 Hz, H-1B), 3.47–3.57 (m, 1H, H-2), 3.99 (dd, 1H, J2,3 = 6.3 Hz, J3,4 = 6.9 Hz, H-3),
5.09 (s, 2H, CH2 in Bn), 5.21 (d, 1H, J4,5A = 11.1 Hz, H-5A), 5.26 (d, 1H, J4,5B = 18.1 Hz, H-5B), 5.83
(ddd, 1H, J3,4 = 6.9 Hz, J4,5A = 10.1 Hz, J4,5B = 17.2 Hz, H-4), 7.25–7.40 (m, 5H, Ph)
13C NMR (75 MHz, CDCl3), δ: –5.0, –4.1 (2q, Si(CH3)2), 18.1 (s, C(CH3)3) 25.8 (q, C(CH3)3), 43.2 (t,
C-1), 66.8 (t, CH2 in Bn), 73.7, 75.4 (2d, C-2, C-3), 117.6 (t, C-5), 126.9, 127.6, 128.5 (all d, Ph), 136.5 (s,
Ph), 137.3 (d, C-4), 156.8 (s, NCO)
MS, m/z (found/calc.): 366.20/366.21 ([M + H]+, C19H32NO4Si)
anti-VIIIa
Yield = 25 % (from VII); [α]2D0 = –3.58◦ (c = 1.575, CHCl3)
FTIR, ν˜/cm−1: 3429, 3344, 2952, 2927, 2856, 1692, 1516, 1471, 1462, 1251, 1077, 1027, 835, 775, 696
1H NMR (300 MHz, CDCl3), δ: 0.05, 0.08 (2s, 2 × 3H, Si(CH3)2), 0.90 (s, 9H, C(CH3)3), 2.55 (bs, 1H,
OH), 3.11 (ddd, 1H, J = 4.1 Hz, J = 7.8 Hz, J1A,1B = 13.3 Hz, H-1A), 3.50 (ddd, 1H, J = 2.9 Hz, J =
7.4 Hz, J1A,1B = 13.3 Hz, H-1B), 3.56–3.67 (m, 1H, H-2), 4.09–4.17 (m, 1H, H-3), 5.10 (s, 2H, CH2 in Bn),
5.17–5.32 (m, 3H, H-5, NH), 5.81 (ddd, 1H, J3,4 = 6.7 Hz, J4,5A = 10.3 Hz, J4,5B = 17.1 Hz, H-4), 7.30–7.38
(m, 5H, Ph)
13C NMR (75 MHz, CDCl3), δ: –5.0, –4.3 (2q, Si(CH3)2), 18.1 (s, C(CH3)3) 25.7 (q, C(CH3)3), 42.7 (t,
C-1), 66.7 (t, CH2 in Bn), 73.4, 76.0 (2d, C-2, C-3), 117.3 (t, C-5), 128.0, 128.1, 128.4, (all d, Ph), 136.5 (s,
Ph), 137.0 (d, C-4), 156.9 (s, NCO)
MS, m/z (found/calc.): 366.20/366.21 ([M + H]+, C19H32NO4Si)
anti-VIa
Yield = 14 % (from VII in the mixture with anti-VIIIa)
1H NMR (300 MHz, CDCl3), δ: 0.02, 0.04 (2s, 2 × 3H, Si(CH3)2), 0.90 (s, 9H, C(CH3)3), 2.85 (bd, 1H, J
= 9.2 Hz, H-2), 3.56–3.66 (m, 2H), 4.02 (bd, 1H, J = 10.5 Hz), 4.51–4.57 (m, 1H), 5.12 (s, 2H, CH2 in Bn),
5.24 (d, 1H, J4,5A = 10.5 Hz, H-5A), 5.34 (d, 1H, J4,5B = 17.3 Hz, H-5B), 5.57 (bd, 1H, J = 6.4 Hz, NH),
5.86 (ddd, 1H, J3,4 = 5.1 Hz, J4,5A = 10.3 Hz, J4,5B = 17.2 Hz, H-4), 7.32–7.37 (m, 5H, Ph)
13C NMR (75 MHz, CDCl3), δ: –5.3, –4.8 (2q, Si(CH3)2), 18.0 (s, C(CH3)3) 25.7 (q, C(CH3)3), 55.2 (d,
C-2), 61.8 (t, C-1), 67.8 (t, CH2 in Bn), 76.0 (d, C-3), 116.6 (t, C-5), 128.1, 128.5, 128.6, (all d, Ph), 136.4
(s, Ph), 137.4 (d, C-4), 156.1 (s, NCO)
MS, m/z (found/calc.): 366.20/366.21 ([M + H]+, C19H32NO4Si)
syn-Va
Yield = 100 %; [α]2D0 = –73.86◦ (c = 1.197, CHCl3), [α]2D0 = –18.33◦ (c = 1.259, CH3OH)
FTIR, ν˜/cm−1: 3329, 3167, 2915, 2848, 1695, 1525, 1466, 1259, 1028, 994, 718, 697
1H NMR (300 MHz, CDCl3), δ: 3.17 (dd, 1H, J1A,2 = 6.5 Hz, J1A,1B = 13.6 Hz, H-1A), 3.23 (bs, 1H, OH),
3.35–3.50 (m, 2H, H-1B, OH), 3.51–3.62 (m, 1H, H-2 or H-3), 3.92–4.04 (m, 1H, H-2 or H-3), 5.08 (s, 2H,
CH2 in Bn), 5.22 (d, 1H, J4,5A = 10.4 Hz, H-5A), 5.33 (d, 1H, J4,5B = 17.2 Hz, H-5B), 5.45 (bs, 1H, NH),
5.86 (1H, ddd, J3,4 = 6.1 Hz, J4,5A = 10.4 Hz, J4,5B = 16.7 Hz, H-4), 7.25–7.38 (m, 5H, Ph)
13C NMR (75 MHz, CDCl3), δ: 43.4 (t, C-1), 67.0 (t, CH2 in Bn), 73.2, 73.6 (2d, C-2, C-3), 117.5 (t, C-5),
128.0, 128.1, 128.5 (all d, Ph), 136.2 (s, Ph), 136.8 (d, C-4), 157.2 (s, NCO)
MS, m/z (found/calc.): 252.10/252.12 ([M + H]+, C13H18NO4)
anti-Va
Yield = 100 %; [α]2D0 = –41.32◦ (c = 1.086, CHCl3), [α]2D0 = –45.07 (c = 1.129, CH3OH)
FTIR, ν˜/cm−1: 3327, 3033, 2895, 1688, 1532, 1454, 1254, 1213, 1001, 741
1H NMR (300 MHz, CDCl3), δ: 3.25–3.42 (m, 4H, H-1, OH), 3.59–3.66 (m, 1H, H-2 or H-3), 4.07 (t, 1H, J
= 5.0 Hz, H-2 or H-3), 5.06 (s, 2H, CH2 in Bn), 5.20 (d, 1H, J4,5A = 10.5 Hz, H-5A), 5.31 (d, 1H, J4,5B
=
17.2 Hz, H-5B), 5.60 (bs, 1H, NH), 5.87 (ddd, 1H, J3,4 = 6.1 Hz, J4,5A = 10.3 Hz, J4,5B = 16.8 Hz, H-4),
7.25–7.35 (m, 5H, Ph)
13C NMR (75 MHz, CDCl3), δ: 42.6 (t, C-1), 66.7 (t, CH2 in Bn), 73.2, 73.9 (2d, C-2, C-3), 117.3 (t, C-5),
128.0, 128.1, 128.4 (all d, Ph), 136.1 (s, Ph), 136.3 (d, C-4), 157.6 (s, NCO)
MS, m/z (found/calc.): 252.10/252.12 ([M + H]+, C13H18NO4)
anti-IIIaa
Yield = 100 %
1H NMR (300 MHz, CDCl3), δ: 3.38 (t, 1H, J = 5.1 Hz, H-2), 3.67–3.75 (m, 2H), 3.94 (dd, 1H, J = 4.0 Hz,
J = 12.0 Hz), 4.35–4.42 (m, 1H), 5.11 (s, 2H, CH2 in Bn), 5.22–5.43 (m, 2H, H-5), 5.65 (bd, 1H, J = 6.8 Hz,
NH), 5.83–5.99 (m, 1H, H-4), 7.32–7.38 (m, 5H, Ph)
13C NMR (75 MHz, CDCl3), δ: 55.2 (d, C-2), 62.1 (t, C-1), 67.0 (t, CH2 in Bn), 74.7 (d, C-3), 116.7 (t,
C-5), 128.1, 128.2, 128.5 (all d, Ph), 136.2 (s, Ph), 137.2 (d, C-4), 156.5 (s, NCO)
MS, m/z (found/calc.): 252.10/252.12 ([M + H]+, C13H18NO4)

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O. Caletková et al./Chemical Papers 67 (1) 66–75 (2013)
Table 1. (continued)
Compound
Physical and spectral data
L-xylo-IXab
Yield = 64 % (from syn-VIIIa); [α]2D0 = –47.7◦ (c = 0.31, MeOH)
Yield = 14 % (2 steps from IV); [α]2D0 = –6.9◦ (c = 1.017, MeOH)
FTIR, ν˜/cm−1: 3381, 2945, 1784, 1674, 1417, 1350, 1216, 1198, 1166, 1116, 1041, 696
1H NMR (600 MHz, CDCl3), δ: 2.67–2.92 (m, 2H, H-4), 3.53–3.62 (m, 1H, H-7A), 3.74, 3.81 (2d, 1H, J7A,7B
= 12.5 Hz, H-7B), 4.47 (bs, 1H, H-8), 4.65, 4.68 (2t, 1H, J1,5 = 5.1 Hz, J4,5 = 5.7 Hz, H-5), 4.78, 4.80 (2d,
1H, J1,5 = 4.3 Hz, H-1), 5.08–5.21 (m, 2H, CH2 in Bn), 7.31–7.39 (m, 5H, Ph)
13C NMR (125 MHz, CDCl3), δ: 34.9, 35.7 (2t, C-4), 52.6, 52.8 (2t, C-7), 56.5, 56.9 (2d, C-5), 67.5, 67.7
(2t, CH2 in Bn), 71.2, 71.9 (2d, C-8), 85.7, 86.5 (2d, C-1), 128.0, 128.2, 128.3, 128.4, 128.6, 128.7 (all d, Ph),
135.9, 136.0 (2s, Ph), 154.4, 154.7 (2s, NCO2), 174.6, 175.0 (2s, C-3)
MS, m/z (found/calc.): 144.10/144.06 ([M – Z + H]+, C6H10NO3)c
L-arabino-IXab Yield = 64 % (from anti-VIIIa); [α]D20 = +15.4◦ (c = 0.967, MeOH), [α]D20 = +18.1◦ (c = 1.00, CHCl3)
Yield = 23 % (2 steps from IV) [α]2D0 = +2.9◦ (c = 1.132, MeOH)
FTIR, ν˜/cm−1: 3400, 2952, 1777, 1678, 1498, 1415, 1356, 1151, 1093, 697
1H NMR (600 MHz, CDCl3), δ: 2.70–2.92 (m, 2H, H-4), 3.34 (dd, 1H, J7A,8 = 7.5 Hz, J7A,7B = 11.3 Hz,
H-7A), 3.41 (dd, 1H, J7A,8 = 6.6 Hz, J7A,7B = 11.6 Hz, H-7A), 3.85–3.90 (m, 1H, H-7B), 4.35–4.39 (m, 1H,
H-8), 4.49 (dt, 1H, J = 3.1 Hz, J = 7.1 Hz, J = 7.1 Hz, H-5), 4.54 (dt, 1H, J = 2.6 Hz, J = 6.7 Hz, J =
6.7 Hz, H-5), 4.93 (t, 1H, J = 5.0 Hz, H-1), 5.07–5.18 (m, 2H, CH2 in Bn), 7.30–7.38 (m, 5H, Ph)
13C NMR (125 MHz, CDCl3), δ: 35.8, 36.5 (2t, C-4), 49.9, 50.4 (2t, C-7), 55.7, 56.3 (2d, C-5), 67.5, 67.6
(2t, CH2 in Bn), 69.7, 70.5 (2d, C-8), 81.6, 82.2 (2d, C-1), 128.0, 128.1, 128.3, 128.4, 128.5, 128.6 (all d, Ph),
135.9 (s, Ph), 154.0, 154.4 (2s, NCO2), 175.2, 175.4 (2s, C-3)
MS, m/z (found/calc.): 144.10/144.06 ([M – Z + H]+, C6H10NO3)c
L-xylo-IIa
Yield = 5 % (2 steps from IV); [α]2D0 = –2.6◦ (c = 1.29, MeOH)
FTIR, ν˜/cm−1: 3313, 3033, 2947, 1782, 1696, 1526, 1454, 1333, 1309, 1231, 1187, 1146, 1069, 1034, 697
1H NMR (600 MHz, CDCl3), δ: 2.63 (d, 1H, J4A,4B = 18.8 Hz, H-4A), 2.74 (dd, 1H, J4B,5 = 6.4 Hz, J4A,4B
= 18.8 Hz, H-4B), 3.81 (d, 1H, J7A,7B = 9.6 Hz, H-7A), 4.03 (dd, 1H, J7B,8 = 4.6 Hz, J7A,7B = 9.7 Hz,
H-7B), 4.33–4.36 (m, 1H, H-8), 4.79–4.84 (m, 1H, H-5), 4.95–4.99 (m, 1H, H-1), 5.12 (s, 2H, CH2 in Bn),
5.16 (bs, 1H, NH), 7.30–7.38 (m, 5H, Ph)
13C NMR (125 MHz, CDCl3), δ: 35.6 (t, C-4), 56.6 (d, C-8), 67.2 (t, CH2 in Bn), 70.7 (t, C-7), 76.9 (d,
C-5), 86.7 (d, C-1), 128.2, 128.4, 128.6 (all d, Ph), 135.8 (s, Ph), 155.5 (s, NCO2), 174.9 (s, C-3)
MS, m/z (found/calc.): 144.10/144.06 ([M – Z + H]+, C6H10NO3)c
L-arabino-IIa
Yield = 56 % (from anti-VIa); [α]D20 = +18.1◦ (c = 1.125, MeOH), [α]D20 = +13.9◦ (c = 1.125, CHCl3)
Yield = 8 % (2 steps from IV); [α]2D0 = +4.3◦ (c = 0.98, MeOH)
FTIR, ν˜/cm−1: 3307, 2952, 1779, 1694, 1531, 1417, 1246, 1187, 1147, 1082, 1070, 976, 900, 839, 738, 696
1H NMR (600 MHz, CDCl3), δ: 2.69 (d, 1H, J4A,4B = 18.9 Hz, H-4A), 2.82 (dd, 1H, J4B,5 = 6.4 Hz, J4A,4B
= 18.9 Hz, H-4B), 3.50 (“t”, 1H, J7A,7B = J7A,8 = 9.3 Hz, H-7A), 4.16 (“t”, 1H, J7A,7B = J7B,8 = 8.2 Hz,
H-7B) 4.48–4.55 (m, 1H, H-8), 4.83 (dd, 1H, J1,5 = 4.3 Hz, J4,5 = 6.4 Hz, H-5), 4.97 (“t”, 1H, J1,5 = J1,8
= 4.3 Hz, H-1) 5.12 (s, 2H, Bn), 5.23 (d, 1H, JNH,8 = 8.0 Hz, NH), 7.31–7.39 (m, 5H, Ph)
13C NMR (125 MHz, CDCl3), δ: 36.6 (t, C-4), 53.7 (d, C-8), 67.3 (t, Bn), 68.9 (t, C-7), 77.3 (d, C-5), 82.1
(d, C-1), 128.1, 128.3, 128.6 (all d, Ph), 135.9 (s, Ph), 155.8 (s, NCO2), 174.7 (s, C-3)
MS, m/z (found/calc.): 144.10/144.06 ([M – Z + H]+, C6H10NO3)c
syn-VIIIb
Yield = 4 % (from VII); [α]2D0 = –1.64◦ (c = 1.094, CHCl3)
FTIR, ν˜/cm−1: 3506, 3275, 2927, 2856, 1599, 1462, 1404, 1327, 1252, 1158, 1090, 835, 777, 664, 551
1H NMR (300 MHz, CDCl3), δ: 0.03, 0.05 (2s, 2 × 3H, Si(CH3)2), 0.86 (s, 9H, C(CH3)3), 2.43 (s, 3H, CH3
in Ts), 2.56 (d, 1H, J2,OH = 4.0 Hz, OH), 2.88 (ddd, 1H, J1A,NH = 5.4 Hz, J1A,2 = 6.8 Hz, J1A,1B
=
12.3 Hz, H-1A), 3.08 (ddd, 1H, J1B,2 = 5.4 Hz, J1B,NH = 6.8 Hz, J1A,1B = 12.3 Hz, H-1B), 3.45–3.53 (m,
1H, H-2), 4.02 (dd, 1H, J1A,NH = 5.4 Hz, J1B,NH = 6.8 Hz, NH), 4.84 (dd, 1H, J2,3 = 6.0 Hz, J3,4 = 7.0 Hz,
H-3), 5.17–5.29 (m, 2H, H-5), 5.73 (ddd, 1H, J3,4 = 7.0 Hz, J4,5A = 10.3 Hz, J4,5B = 17.3 Hz, H-4), 7.31
(d, 2H, J = 8.1 Hz, Ts), 7.73 (d, 2H, J = 8.3 Hz, Ts)
13C NMR (75 MHz, CDCl3), δ: –5.0, –4.1 (2q, Si(CH3)2), 18.1 (s, C(CH3)3), 21.5 (q, CH3 in Ts), 25.7 (q,
C(CH3)3), 44.7 (t, C-1), 72.6, 75.2 (2d, C-2, C-3), 118.2 (t, C-5), 127.1, 129.7, 136.9 (all d, Ph, C-4), 136.5,
143.5 (2s, Ph)
MS, m/z (found/calc.): 386.20/386.17 ([M + H]+, C18H32NO4SSi)

O. Caletková et al./Chemical Papers 67 (1) 66–75 (2013)
71
Table 1. (continued)
Compound
Physical and spectral data
anti-VIIIb
Yield = 18 % (from VII); [α]2D0 = –12.33◦ (c = 1.088, CHCl3)
FTIR, ν˜/cm−1: 3494, 3275, 2954, 2927, 2856, 1599, 1495, 1471, 1402, 1324, 1252, 1157, 1090, 835, 777, 662,
551
1H NMR (300 MHz, CDCl3), δ: 0.02, 0.05 (2s, 2 × 3H, Si(CH3)2), 0.87 (s, 9H, C(CH3)3), 2.33 (d, 1H,
J2,OH = 4.0 Hz, OH), 2.43 (s, 3H, CH3 in Ts), 2.89 (ddd, 1H, J1A,NH = 3.5 Hz, J1A,2 = 7.5 Hz, J1A,1B
=
12.7 Hz, H-1A), 3.18 (ddd, 1H, J1B,NH = 3.5 Hz, J1B,2 = 8.6 Hz, J1A,1B = 12.4 Hz, H-1B), 3.55 (ddd, 1H,
J2,OH = 4.0 Hz, J1A,2 = 7.5 Hz, J1A,2 = 8.6 Hz, H-2), 4.10 (dd, 1H, J1A,NH = 3.5 Hz, J1B,NH = 4.9 Hz,
NH), 5.01–5.10 (m, 1H, H-3), 5.15–5.26 (m, 2H, H-5), 5.69 (ddd, 1H, J3,4 = 6.5 Hz, J4,5A = 10.4 Hz, J4,5B
= 17.1 Hz, H-4), 7.31 (d, 2H, J = 8.1 Hz, Ts), 7.73 (d, 2H, J = 8.2 Hz, Ts)
13C NMR (75 MHz, CDCl3), δ: –5.0, –4.4 (2q, Si(CH3)2), 18.0 (s, C(CH3)3), 21.5 (q, CH3 in Ts), 25.7 (q,
C(CH3)3), 44.6 (t, C-1), 72.2, 76.0 (2d, C-2, C-3), 117.7 (t, C-5), 127.1, 129.7, 136.7 (all d, Ph, C-4), 136.6,
143.4 (2s, Ph)
MS, m/z (found/calc.): 386.20/386.17 ([M + H]+, C18H32NO4SSi)
anti-VIb
Yield = 8 % (from VII); [α]2D0 = +12.46◦ (c = 1.046, CHCl3)
FTIR, ν˜/cm−1: 3510, 3284, 2953, 2928, 2885, 2856, 1598, 1471, 1404, 1327, 1252, 1158, 1089, 835, 813, 778,
665, 551
1H NMR (300 MHz, CDCl3), δ: 0.02, 0.09 (2s, 2 × 3H, Si(CH3)2), 0.88 (s, 9H, C(CH3)3), 2.41 (s, 3H, CH3
in Ts), 2.65 (dd, 1H, J = 2.5 Hz, J = 9.9 Hz, H-2), 3.12 (ddd, 1H, J = 3.4 Hz, J = 3.5 Hz, J = 11.1 Hz,
H-1A), 3.25 (ddd, 1H, J = 3.9 Hz, J = 10.1 Hz, J = 13.9 Hz, H-1B), 3.84 (dt, 1H, J = 2.8 Hz, J = 2.8 Hz, J
= 11.7 Hz), 4.39–4.45 (m, 1H, H-3), 5.16–5.32 (m, 2H, H-5), 5.73 (ddd, 1H, J3,4 = 5.7 Hz, J4,5A = 10.5 Hz,
J4,5B = 17.1 Hz, H-4), 7.30 (d, 2H, J = 8.1 Hz, Ts), 7.76 (d, 2H, J = 8.3 Hz, Ts)
13C NMR (75 MHz, CDCl3), δ: –5.0, –4.7 (2q, Si(CH3)2), 18.0 (s, C(CH3)3), 21.5 (q, CH3 in Ts), 25.7 (q,
C(CH3)3), 57.7 (d, C-2), 61.3 (t, C-1), 77.1 (d, C-3), 117.2 (t, C-5), 127.1, 129.7, 137.0, 137.4, 143.6 (Ph,
C-4)
MS, m/z (found/calc.): 386.20/386.17 ([M + H]+, C18H32NO4SSi)
syn-Vb
Yield = 100 %; [α]D20 = –6.429◦ (c = 1.454, CHCl3)
FTIR, ν˜/cm−1: 3255, 2924, 2854, 1712, 1597, 1495, 1427, 1400), 1319, 1153, 1086, 1032, 1005, 813, 661, 549
1H NMR (300 MHz, CD3OD), δ: 2.43 (s, 3H, CH3 in Ts), 2.80 (dd, 1H, J1A,2 = 7.6 Hz, J1A,1B = 13.0 Hz,
H-1A), 3.02 (dd, 1H, J1B,2 = 4.6 Hz, J1A,1B = 13.0 Hz, H-1B), 3.52 (td, 1H, J1B,2 = 4.6 Hz, J2,3 = 4.6 Hz,
J1A,2 = 7.6 Hz, H-2), 4.00 (tdd, 1H, J3,5A = J3,5B = 1.5 Hz, J2,3 = 4.6 Hz, J3,4 = 6.0 Hz, H-3), 5.14 (td,
1H, J3,5A = J5A,5B = 1.5 Hz, J4,5A = 10.5 Hz, H-5A), 5.26 (td, 1H, J3,5B = J5A,5B = 1.5 Hz, J4,5B
=
17.3 Hz, H-5B), 5.86 (ddd, 1H, J3,4 = 6.0 Hz, J4,5A = 10.5 Hz, J4,5B = 16.8 Hz, H-4), 7.38 (d, 2H, J =
8.1 Hz, Ts), 7.73 (d, 2H, J = 8.3 Hz, Ts)
13C NMR (75 MHz, CD3OD), δ: 21.5 (q, CH3 in Ts), 46.5 (t, C-1), 74.1, 74.6 (2d, C-2, C-3), 116.7 (t, C-5),
128.1, 130.8 (all d, Ph), 138.7 (s, Ph), 138.9 (d, C-4), 144.7 (s, Ph)
MS, m/z (found/calc.): 272.00/272.09 ([M + H]+, C12H18NO4S)
anti-Vb
Yield = 100 %; [α]D20 = –7.98◦ (c = 0.978, CHCl3)
FTIR, ν˜/cm−1: 3444, 3276, 2992, 2873, 1597, 1495, 1427, 1402, 1319, 1152, 1089, 813, 660, 549
1H NMR (300 MHz, CDCl3), δ: 2.42 (s, 3H, CH3 in Ts), 3.02 (dd, 1H, J1A,2 = 7.0 Hz, J1A,1B = 13.4 Hz,
H-1A), 3.13 (dd, 1H, J1B,2 = 3.4 Hz, J1A,1B = 13.4 Hz, H-1B), 3.67–3.75 (m, 1H, H-2), 4.21 (dd, 1H, J2,3
= 5.0 Hz, J3,4 = 6.0 Hz, H-3), 5.23 (d, 1H, J4,5A = 10.5 Hz, H-5A), 5.32 (d, 1H, J4,5B = 17.3 Hz, H-5B),
5.82 (ddd, 1H, J3,4 = 6.1 Hz, J4,5A = 10.5 Hz, J4,5B = 16.9 Hz, H-4), 7.30 (d, 2H, J = 8.2 Hz, Ts), 7.73
(d, 2H, J = 8.2 Hz, Ts)
13C NMR (75 MHz, CDCl3), δ: 21.5 (q, CH3 in Ts), 44.3 (t, C-1), 72.3, 74.1 (2d, C-2, C-3), 117.8 (t, C-5),
127.0, 129.8 (all d, Ph), 135.9 (d, C-4), 136.4, 143.6 (all s, Ph)
MS, m/z (found/calc.): 272.00/272.09 ([M + H]+, C12H18NO4S)
anti-IIIb
Yield = 100 %; [α]D20 = –2.735◦ (c = 1.077, CHCl3)
FTIR, ν˜/cm−1: 3423, 3271, 2924, 1714, 1599, 1427, 1402, 1320, 1306, 1152, 1089, 1034, 929, 813, 662, 547
1H NMR (300 MHz, CD3OD), δ: 2.42 (s, 3H, CH3 in Ts), 3.21 (ddd, 1H, J1A,2 = 5.1 Hz, J1B,2 = 5.1 Hz,
J2,3 = 5.9 Hz, H-2), 3.43 (dd, 1H, J1A,2 = 5.1 Hz, J1A,1B = 11.3 Hz, H-1A), 3.57 (dd, 1H, J1B,2 = 5.0 Hz,
J1A,1B = 11.3 Hz, H-1B), 4.08 (tt, 1H, J3,5A = 1.5 Hz, J3,5B = 1.5 Hz, J2,3 = 5.9 Hz, J3,4 = 5.9 Hz, H-3),
5.05 (dt, 1H, J3,5A = 1.5 Hz, J5A,5B = 1.5 Hz, J4,5A = 10.5 Hz, H-5A), 5.21 (d, 1H, J3,5B = 1.5 Hz, J5A,5B
= 1.5 Hz, J4,5B = 17.2 Hz, H-5B), 5.75 (ddd, 1H, J3,4 = 6.1 Hz, J4,5A = 10.5 Hz, J4,5B = 16.9 Hz, H-4),
7.39 (d, 2H, J = 8.2 Hz, Ts), 7.76 (d, 2H, J = 8.2 Hz, Ts)
13C NMR (75 MHz, CD3OD), δ: 21.5 (q, CH3 in Ts), 60.6 (d, C-2), 62.0 (t, C-1), 73.7 (d, C-3), 116.7 (t,
C-5), 128.2, 130.6 (all d, Ph), 139.1 (d, C-4), 140.1, 144.5 (all s, Ph)
MS, m/z (found/calc.): 272.00/272.09 ([M + H]+, C12H18NO4S)

72
O. Caletková et al./Chemical Papers 67 (1) 66–75 (2013)
Table 1. (continued)
Compound
Physical and spectral data
L-xylo-IXb
Yield = 80 % (from syn-VIIIb); [α]2D0 = +2.3◦ (c = 0.87, CH3OH)
FTIR, ν˜ /cm−1: 3483, 2920, 1782, 1598, 1456, 1401, 1337, 1155, 1089, 1042, 813, 656, 588, 545
1H NMR (300 MHz, CDCl3), δ: 2.45 (s, 3H, CH3 in Ts), 2.82 (dd, 1H, J4A,5 = 6.5 Hz, J4A,4B = 18.6 Hz, H-4A),
2.97 (d, 1H, J4A,4B = 18.6 Hz, H-1B), 3.50 (d, 1H, J7A,7B = 12.5 Hz, H-7A), 3.66 (dd, 1H, J7B,8 = 3.8 Hz,
J7A,7B = 12.5 Hz, H-7B), 4.41–4.46 (m, 1H, H-8), 4.50 (dd, 1H, J1,5 = 5.7 Hz, J4A,5 = 6.5 Hz, H-5), 4.71 (d,
1H, J1,8 = 5.2 Hz, J1,5 = 5.7 Hz, H-1), 7.35 (d, 2H, J = 8.1 Hz, Ts), 7.74 (d, 2H, J = 8.3 Hz, Ts)
13C NMR (75 MHz, CDCl3), δ: 21.6 (q, CH3 in Ts), 36.2 (t, C-4), 54.5 (t, C-7), 58.6 (d, C-5), 72.4 (d, C-8),
86.6 (d, C-1), 127.6, 129.9 (all d, Ph), 134.4, 144.4 (all s, Ph), 174.3 (s, C-3)
MS, m/z (found/calc.): 298.10/298.07 ([M + H]+, C13H16NO5S)
L-arabino-IXb Yield = 83 % (from anti-VIIIb); [α]2D0 = +18.7◦ (c = 1.08, CH3OH); m.p. = 138–140◦C
FTIR, ν˜/cm−1: 3421, 2889, 1756, 1599, 1496, 1471, 1404, 1341, 1160, 1090, 938, 660, 575, 539
1H NMR (600 MHz, CDCl3), δ: 2.46 (s, 3H, CH3 in Ts), 2.87–2.89 (m, 2H, H-4), 3.46 (dd, 1H, J7A,8 = 6.1 Hz,
J7A,7B = 11.1 Hz, H-7A), 3.50 (dd, 1H, J7B,8 = 5.8 Hz, J7A,7B = 11.1 Hz, H-7B), 4.09–4.14 (m, 1H, H-8), 4.29
(d, 1H, JOH,8 = 6.5 Hz, OH), 4.38 (m, 1H, H-5), 4.81 (dd, 1H, J = 4.4 Hz, J = 6.7 Hz H-1), 7.38 (d, 2H, J =
8.1 Hz, Ts), 7.73 (d, 2H, J = 8.3 Hz, Ts)
13C NMR (125 MHz, CDCl3), δ: 21.5 (q, CH3 in Ts), 37.0 (t, C-4), 52.3 (t, C-7), 57.7 (d, C-5), 70.0 (d, C-8),
81.9 (d, C-1), 127.4, 130.2 (all d, Ph), 134.4, 144.4 (all s, Ph), 175.1 (s, C-3)
MS, m/z (found/calc.): 298.10/298.07 ([M + H]+, C13H16NO5S)
L-arabino-IIb Yield = 76 % (from anti-VIb); [α]2D0 = +85.1◦ (c = 1.15, CHCl3), [α]D20 = +66.9◦ (c = 1.19, CH3OH)
FTIR, ν˜/cm−1: 3500, 3249, 2925, 2856, 1779, 1599, 1452, 1330, 1155, 1084, 1057, 814, 662, 544
1H NMR (600 MHz, CD3OD), δ: 2.43 (s, 3H, CH3 in Ts), 2.48 (d, 1H, J4A,4B = 18.8 Hz, H-4A), 2.84 (dd, 1H,
J4B,5 = 5.9 Hz, J4A,4B = 18.7 Hz, H-4B), 3.39 (dd, 1H, J7A,7B = 8.9 Hz, J7A,8 = 9.7 Hz, H-7A), 3.77 (dd, 1H,
J7B,8 = 7.7 Hz, J7A,7B = 8.6 Hz, H-7B), 4.05 (ddd, 1H, J1,8 = 4.4 Hz, J7B,8= 7.7 Hz, J7A,8 = 9.7 Hz, H-8),
4.67–4.73 (m, 2H, H-5, H-1), 7.39 (d, 2H, J = 8.1 Hz, Ts), 7.80 (d, 2H, J = 8.3 Hz, Ts)
13C NMR (125 MHz, CD3OD), δ: 21.5 (q, CH3 in Ts), 37.5 (t, C-4), 56.9 (d, C-8), 69.3 (t, C-7), 79.0 (d, C-5),
83.6 (d, C-1), 128.2, 130.9 (all d, Ph), 139.6, 145.0 (all s, Ph), 177.6 (s, C-3)
MS, m/z (found/calc.): 298.10/298.07 ([M + H]+, C13H16NO5S)
a) All data were determined from the mixture with anti-Va; b) mixture of conformers; c) for Z, see Table 2.
Table 2. Influence of ligand structure, solvent, and chloramine substituents on asymmetric hydroxyamination of I
anti-V/syn-V/anti-III/syn-IIIa
VIII/syn-VIII/anti-VI/syn-VIa
Entry
R
R1
Ligand
Solvent
Yieldb/%
1
2
3
4
5
6
7
8
9
10
11
12
13
H
H
H
H
Z
Z
Z
Z
Ts
Z
Z
Z
Z
Ts
Ts
Ts
Ts
(DHQD)2Phal
(DHQD)2AQN
(DHQD)2Phal
(DHQD)2AQN
(DHQD)2Phal
(DHQD)2Phal
(DHQD)2AQN
(DHQD)2Phal
(DHQD)2AQN
(DHQD)2Phal
(DHQD)2AQN
(DHQD)2Phal
(DHQD)2AQN
n-PrOH
n-PrOH
CH3CN
CH3CN
n-PrOH
n-PrOH
n-PrOH
CH3CN
CH3CN
n-PrOH
n-PrOH
CH3CN
CH3CN
6/3/1/ < 0.5
13/6/1/ < 0.5
7/3/1/ < 0.5
5/2/1/ < 0.5
6/3/1/ < 0.5
3/2/1/ < 0.5
3/1/1/ < 0.5
5/3/1/ < 0.5
4/3/1/ < 0.5
3/1/1/ < 0.5
2/1/1/ < 0.5
5/3/1/ < 0.5
4/3/1/ < 0.5
82
60
56
54
57
42
65
42
45
53
42
48
55
H
TBS
TBS
TBS
TBS
TBS
TBS
TBS
TBS
a) Ratio of stereomers was estimated on the basis of 13C NMR spectral data of crude reaction mixtures; b) overall yield.
tones l-arabino-IIa, -IIb, l-arabino-IXa, -IXb, and
l-xylo-IXa, -IXb, respectively, with high regio- and
threo-selectivity in moderate to good yields (Fig. 3).
In addition, when the mixture of all isomers III
and V underwent oxycarbonylation, all four prod-
ucts II and IX were successfully separated, albeit
with decreased optical purity. The configuration of
pyrrolidinolactones l-arabino-IXa, -IXb and l-xylo-
IXa, -IXb was established by comparing the 1H
NMR data and specific rotation with the litera-
ture data of N-benzyloxycarbonyl-2,3,6-trideoxy-3,6-
imino-d-arabino-1,4-hexonolactone (Jäger & Hu¨m-
mer, 1990; Hu¨mmer et al., 1997; [α]2D2 –71.6◦ (c =
0.666, CHCl3)). These pyrrolidinolactones serve as
precursors for syntheses of hydroxypyrrolidines (1,4-
iminoglycitols) known to show high activity against
glycosidases (Fleet et al., 1985; Bashyal et al., 1987;
Winkler & Holan, 1989). 3,6-Anhydro-2,5-dideoxy-5-

O. Caletková et al./Chemical Papers 67 (1) 66–75 (2013)
73
Fig. 3. Domino Pd(II)-cyclisation/oxycarbonylation reaction of V and III. Reaction conditions: i) PdCl2 (0.1 eq), CuCl2 (3 eq),
AcONa (3 eq), AcOH, CO (balloon).
benzyloxyamino-l-arabino-1,4-hexonolactone (l-ara-
bino-IIa) is an intermediate in the synthesis of 2-epi-
jaspine B from l-serine (Bhaket et al., 2005).
signment, Tetrahedron: Asymmetry, 19, 1027–1047. DOI:
10.1016/j.tetasy.2008.04.017.
Angelaud, R., Landais, Y., & Schenk, K. (1997). Asymmet-
ric amino-hydroxylation of dienylsilanes. An efficient route
to amino-cyclitols. Tetrahedron Letters, 38, 1407–1410. DOI:
10.1016/s0040-4039(97)00079-8.
Conclusions
Babjak, M., Kapitán, P., & Gracza, T. (2002). The first total
synthesis of goniothalesdiol. Tetrahedron Letters, 43, 6983–
6985. DOI: 10.1016/s0040-4039(02)01599-x.
In conclusion, the present study shows that the
Sharpless aminohydroxylation may be applied to both
protected and unprotected divinylcarbinol so as to
furnish all isomers of aminopent-4-enediol intermedi-
ates for organic synthesis. The transformation pro-
ceeds with anti-diastereoselectivity (up to 4 : 1) and
good regioselectivity (up to 19 : 1) in favour of 1-
amino regioisomers V and VIII. The Pd(II)-catalysed
oxy- and amidocarbonylation of aminopent-4-enediols
III and V provided regio- and diastereoselectively
lactones IX and X, respectively. The synthetic ap-
proach was applied in a short formal synthesis of 2-
epi-jaspine B. In addition, the bicyclic pyrrolidinolac-
tones l-arabino-IXa, -IXb and l-xylo-IXa, -IXb con-
stitute new types of unnatural proline analogues, i.e.
dihydroxy-homoproline derivatives.
Babjak, M., Kapitán, P., & Gracza, T. (2005). Synthesis of
(+)-goniothalesdiol and (+)-7-epi-goniothalesdiol. Tetrahe-
dron, 61, 2471–2479. DOI: 10.1016/j.tet.2005.01.004.
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86850-2.
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J., & Delgado, A. (2009). Synthesis and biological proper-
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Acknowledgements. This work was financially supported by
the Slovak grant agencies (VEGA, Slovak Academy of Sciences
and Ministry of Education, Bratislava, project no. 1/0236/09;
APVV, Bratislava, project no. APVT-0203-10, and ASFEU,
Bratislava, ITMS projects nos. 26240120001, 26240120025).
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