Synthesis and structure of tetratosyl bora derivatives of resorcinarenes from L-proline and L-prolinol

Full text of DOI:10.1080/00304940902955939

Organic Preparations and Procedures International, 41:217–227, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 0030-4948 print
DOI: 10.1080/00304940902955939
Synthesis and Structure of Tetratosyl Bora
Derivatives of Resorcinarenes From L-Proline
and L-Prolinol
Barbara Gawdzik,1 Alicja Wzorek,1 Jochen Mattay,2
and Waldemar Iwanek1
1
´
Jan Kochanowski University, Institute of Chemistry, Swietokrzyska 15G,
ꢀ
25406 Kielce, Poland
2Fakulta¨t fu¨r Chemie, Universita¨t Bielefeld, Universita¨tsstr. 25,
33615 Bielefeld, Germany
Organoboron compounds play an important role in asymmetric synthesis. In particular, the
oxazaborolidines are highly useful as excellent chiral catalysts for the asymmetric reduc-
tion of prochiral ketones as well as for the other enantioselective reactions.1–4 Formation of
strong intramolecular coordinate bonds between the nitrogen and the boron atoms provides
many possibilities for the synthesis of new hetero- or macrocyclic compounds.5–9 In addi-
tion, some of these compounds have been recognized as biologically active substances.10 Ex-
amples of the synthesis of chiral boron derivatives of resorcinarene have been reported.11–14
Herein we describe the synthesis of new chiral di-boron derivatives of resorcinarenes from
tetratosylresorcinarene, l-proline and l-prolinol.
The reaction of resorcinarene 1 with tosyl chloride in the presence of triethylamine gave
the tetratosyl derivative of resorcinarene 2 in good yields (67%),15 as shown in Scheme 1,
that is consistent with the literature data.
HO
OH
HO
OH
HO
HO
TosO
TosO
OH
OH
OTos
OTos
TosCl
Et3N
HO
OH
HO
OH
2
1
Scheme 1
Received October 2, 2008; in final form March 20, 2009
Address correspondence to Waldemar Iwanek, Jan Kochanowski University, Institute of Chem-
´
istry, Swietokrzyska 15G, 25406 Kielce, Poland. E-mail: iwanek@ujk.kielce.pl
ꢀ
217

218
Iwanek et al.
The resulting tetratosylresorcinarene 2 was converted into new disubstituted chiral
products 3a and 3b using l-proline and l-prolinol according to Scheme 2.
X
N
OH
OH
HO
HO
OH
OH
HO
HO
OH
X
TosO
TosO
TosO
OTos
OTos
OTos
; HCHO
HN
EtOH
TosO
HO
OTos
OH
N
2
X
3a X = CO
3b X = CH2
Scheme 2
bis-l-Proline-tetratosylresorcinarene (3a) and bis-l-prolinol-tetratosylresorcinarene
(3b) were synthesized by standard Mannich reaction using formaldehyde and correspond-
ingly l-proline and l-prolinol. The reaction was carried out in ethanol under reflux for 4
hours. After cooling the reaction mixture to room temperature, spectrally pure l-proline
derivatives of tetratosyloresorcinarene 3a precipitated as a colorless solid, while the pure
l-prolinol derivatives of tetratosylresorcinarenes 3b were obtained by recrystallization
from chloroform. The spectral data of these compounds are given in the Experimental
Section. These l-proline and l-prolinol derivatives 3a and 3b having an electron lone
pair at the nitrogen atom and the free hydroxy groups were then used for reaction with
selected boron compounds such as boric acid, phenylboric acid, 3-chlorophenylboric acid,
3,5-dibromophenylboric acid as well as with trimethyl borate (Scheme 3). In all of these
X
X
O
N
N
B
OH
R1
HO
OH
HO
O
TosO
TosO
OTos
OTos
R1R2R3B
MeCN
TosO
HO
TosO
R1
OTos
OTos
HO
OH
O
B
OH
N
N
O
X
X
3a X = CO
3b X = CH2
4a-h
Scheme 3

Synthesis and Structure of Bora Derivatives of Resorcinarenes
219
Table 1
Boron Derivatives of Tetratosylresorcinarenes 4a–h
Product
X
R1
R2
R3
out-(M,S,R,SN,RB) (4a)
out-(M,S,R,SN,SB) (4b)
out-(M,S,R,SN,SB) (4c)
out-(M,S,R,SN,SB) (4d)
out-(M,S,R,SN,RB) (4e)
out-(M,S,R,SN,RB) (4f)
out-(M,S,R,SN,RB) (4g)
out-(M,S,R,SN,RB) (4h)
C=O
C=O
C=O
C=O
C=O
CH2
OH
Ph
3-ClC6H5
3,5-Br2C6H4
OMe
OH
OH
OH
OH
OMe
OH
OH
OH
OH
OH
OH
OH
OMe
OH
OH
OH
Ph
CH2
CH2
3-ClC6H5
3,5-Br2C6H4
reactions compounds 3a and 3b, by formation of a coordinate bond between the boron and
the nitrogen atoms, afforded novel boron derivatives of the tetratosylresorcinarene 4a–h
containing bora-oxazine-oxazolidinone or bora-oxazine-oxazolidine rings (Table 1).
Reactions using bis-l-proline-tetratosylresorcinarene 3a were carried out in acetonitrile
heated at reflux while the reactions using bis-l-prolinol-tetratosylresorcinarene 3b were
performed in toluene with azeotropic removal of water from the reaction mixture.
The structures of all boron derivatives of the tetratosylresorcinarene 4a–h were con-
firmed by 1H and 13C NMR spectroscopy and in addition, by two-dimensional 1H,1H-COSY
1
and H,1H-NOESY experiments confirming their spatial structure. In all reactions, the
boat conformer of out-(M,S,R)-bora-oxazine-oxazolidinone or out-(M,S,R)-bora-oxazine-
oxazolidine derivatives of tetratosylresorcinarene were obtained (according to stereochemi-
cal nomenclature proposed for C4 symmetric compounds reported in the literature16,17), with
the bora-oxazine rings oriented outside of the resorcinarene cavity (Isomerism “in-out”).18
Such arrangement of rings cause the phenyl groups attached to boron atoms to point to the
1
inside of the resorcinarene cavity. There is the most important part of the H,1H-NOESY
spectrum (500 MHz) of bora-oxazine-oxazolidinone derivative 4d with marked signals of
coupling protons indicating the spatial structure of this compound in Figure 1 . The compar-
ison of the location of the signal of the methine proton H1 of the l-proline moiety in the 1H
NMR spectrum (CDCl3) of the bis-bora-l-proline-tetratosyl derivative 4d and of l-proline
derivative 3a allowed us to rationalize that bora-oxazolidinone rings or the bora-oxazolidine
rings in all of the boron derivatives are oriented outside of the resorcinarene cavity (iso-
mer out). The methine signals of 4d located at δ 3.92 is shifted downfield in comparison
to the corresponding signal of 3a (δ 3.67). The coupling in NOESY spectra of 4d between
the methine proton H1 and the aminomethylene protons H9 and between the aminomethy-
lene protons H8 and the l-proline proton H7 lead to the conclusion that, in all the reactions,
the isomers out-(M,S,R) of the bora-tetratosylresorcinarenes were obtained (Figure 1).
These couplings are possible only when the bora-oxazine rings are closed in proposed
direction and if the rings are oriented outside of the resorcinarene cavity.
In all of the reactions performed using l-proline-tetratosylresorcinarene 3a as well as
l-prolinol-tetratosylresorcinarene 3b, two new stereogenic centers were generated at the
boron atom and at the nitrogen atom as a result of forming bora-oxazine-oxazolidinone rings

220
Iwanek et al.
H3
H5
H2
H4
O
(S)
H1
H6
H7
Br
O
N
B
H9
H8
HO
Br
O
Tos O
OTos
Tos O
Br
OTos
O
B
OH
Br
N
O
O
H1
H8
H9
H6
H2H3
H7
H4H5
H5
H4
2.0
3.0
4.0
5.0
H2H3
H6
H7
O
H8
H1
O
O
H9
O
6.0
ppm (t1
5.00
4.50
4.00
3.50
3.00
2.50
2.00
1.50
ppm (t2)
1
Figure 1. The most important portion of the H,1H-NOESY spectra (500 MHz) of bora–oxazine-
oxazolidinone derivative 4d.
or bora-oxazine-oxazolidine rings. In the case of the diastereoisomers 4b–e, the nitrogen
and boron atoms are of the S-configuration while in the case of 4a and 4f–h the nitrogen
and boron atoms adopt S- and R-configurations respectively as shown in Table 1.
In conclusion this paper describes novel bis-l-proline and bis-l-prolinol deriva-
tives of tetratosylresorcinarene synthesized via Mannich reaction from formaldehyde and

Synthesis and Structure of Bora Derivatives of Resorcinarenes
221
respectively l-proline and l-prolinol as well as the novel boron derivatives of tetratosylre-
sorcinarene as results of reaction of these derivatives with boron compounds. The structures
all of the received derivatives were confirmed by NMR-spectroscopy. In all of reactions, the
conformer of out-bora-oxazine-oxazolidinone or out-bora-oxazine-oxazolidine derivatives
of tetratosylresorcinarene was obtained with two new stereogenic centers at the boron and
the nitrogen atoms. The phenyl groups linked to the boron atoms are oriented toward the
resorcinarene cavity.
Experimental Section
All 1H- and 13C NMR, 2D NMR ((1H,1H-COSY and 1H,1H-NOESY) spectra were measured
at 499.893 MHz, on a Bruker DRX 500 spectrometer. Mass spectra were recorded on an
Esquire 3000 ion trap mass spectrometer (Bruker Daltonik) and on a Bruker APEX III FT
MS at the University in Bielefeld, with the electrospray (ES) technique. Melting points
were determined with a Boe¨tius melting point instrument and are uncorrected. Optical
rotation values were measured on an Optical Perkin–Elmer 341 Model polarimeter that
was operated at λ 589 nm, which corresponds to the sodium D line at 25◦C. Elemental
analyses were performed by a Perkin–Elmer 2400 model instruments. All chromatographic
manipulations used silica gel 60 (SiO2, Merck, particle size 0.040–0.063 mm, 230–240
mesh) as the adsorbent. Reactions were monitored by thin layer chromatography (TLC) on
plastic sheets coated with Merck Kieselgel 60 F254 silica gel. TLC plates were visualized
by UV radiation at a wavelength of 254 nm. Reagents and solvents were obtained from
Fluka and Merck and were used without purification.
Procedure for Tetratosylresorcinarene (2)
To a solution of resorcinarenes 1 (10 mmol, 5.45 g) in MeCN (100 ml), was added anhydrous
Et3N (40 mmol, 4.04 g) and the mixture was stirred at 25◦C for 15 min. A solution of tosyl
chloride (40 mmol, 7.68 g) in MeCN (50 ml) was added and the reaction mixture was stirred
for 12 hours. The precipitated solid was collected and washed with MeCN (2 × 20 ml),
water (20 ml), and then was dissolved in DMF (50 ml) and extracted with water-CHCl3.
The organic layer was dried with MgSO4. After solvent removal the pure product was
obtained as a colorless solid (7.73 g, 67%) mp. 311–312◦C, lit.15 mp. 310–313◦C).
Procedure for bis-L-Proline- and bis-L-Prolinoltetratosyloresorincarene (3a and 3b)
To a warm solution of tetratosylresorcinarene 2 (4.3 mmol, 5.00 g), l-prolinol (8.7
mmol,0.90 ml) or l-proline (8.7 mmol, 1.00 g) in EtOH (120 ml), formaldehyde (8.7
mmol, 0.09 ml) was added and the mixture was refluxed gently. After 4 h, the reaction
mixture was cooled to 25◦C. In the case of reaction with l-proline, the precipitated white
solid was collected and washed with EtOH to afford spectrally pure product. In the case
of reaction using l-prolinol, the solvent was removed under vacuum and the residue was
purified by crystallization from CHCl3.
bis-L-Prolinetetratosylresorcinarene (3a), 70% yield, mp. 193–194◦C, [α]D25 = −5◦
(CH3OH, c 0.138).

222
Iwanek et al.
1H NMR (500 MHz) [CDCl3, 25◦C): δ 1.58 (d, J = 6.9Hz, 6H, -CH3), 1.61 (d, J =
6.9Hz, 6H, -CH3), 1.69 (m, 1H, H5), 1.86 (m, 1H, H4), 1.94 (m, 1H, H3), 2.26 (m, 1H,
H2), 2.82 (s, 6H, Ar-CH3), 2.88 (s, 6H, Ar-CH3), 2.87 (q, J = 8.0Hz, 1H, H7), 3.16 (m,
1H, H6), 3.67 (dd, J = 8.0,4.0Hz, 1H, H1), 3.76 (s, 4H, -OH), 3.96 (d, J = 16.0Hz, 2H,
H8), 4.03 (d, J = 12.0Hz, 2H, H9), 4.74 (k, J = 6.9Hz, 2H, -CHCH3), 4.80 (q, J = 6.9Hz,
2H, -CHCH3), 6.14 (s, 2H, ArH), 7.88 (m, 3H, ArH), 8.16 (d, J = 6.9Hz, 8H, ArH), 8.19
(d, J = 6.9Hz, 8H, ArH).
13C NMR (500 MHz) DMSO-d6, 25◦C): δ 20.57, 20.87, 21.23, 22.68, 28.69, 30.20,
30.35, 49.64, 52.31, 65.94, 109.04, 113.18, 121.91, 122.23, 123.85, 127.97, 128.03, 130.33,
132.41, 138.14, 143.98, 144.03, 145.80, 151.46, 152.35, 175.35.
EI-MS (70 eV): m/z (%): 1415,6346.
IR [cm−1]: (600, 724, 844, 920, 1008, 1136, 1184, 1192, 1320, 1556, 1600, 3000,
3480).
Anal. Calcd for C72H74N2O20S4: C, 61.09; H, 5.27; N, 1.78; S, 9.06.
Found: C, 60.98; H, 5.29; N, 1.81; S, 9.08.
bis-L-Prolinoltetratosylresorcinarene (3b), 65% yield, mp. 197–198 ◦C, [α]D25 = +59◦
(CHCl3, c 0.276).
1H NMR (500 MHz) CDCl3, 25◦C): δ 1.31 (d, J = 6.9Hz, 6H, -CH3), 1.38 (d, J =
6.9Hz, 6H, -CH3), 1.90 (m, 4H, H5,H4,H3), 2.00 (m, 2H, H2), 2.38 (m, 2H, H6), 2.42
(s, 6H, Ar-CH3), 2.44 (s, 6H, Ar-CH3), 3.05 (m,2H, H7), 3.28 (m, 2H, H1), 3.78 (m, 4H,
CH2OH), 4.16 (d, J = 13.5Hz, 2H, H8), 4.33 (d, J = 13.5Hz, 2H, H9), 4.43 (m, 4H,
-CHCH3), 6.02 (s, 2H, ArH), 6.57 (s, 2H, ArH), 7.08 (s, 2H, ArH), 7.38 (d, J = 8.0Hz, 4H,
ArH), 7.40 (d, J = 8.0Hz, 4H, ArH), 7.85 (d, J = 8.0Hz, 4H, ArH), 7.87 (d, J = 8.0Hz,
4H, ArH).
13C NMR (500 MHz) CDCl3, 25◦C): δ 19.78, 19.94, 21.81, 21.84, 22.77, 25.66, 25.96,
30.68, 32.60, 32.70, 45.75, 52.92, 60.64, 67.71, 76.75, 77.00, 77.26, 108.69, 115.59, 122.95,
126.67, 127.01, 128.46, 128.55, 130.35, 130.42, 131.91, 132.30, 138.86, 139.63, 145.11,
145.32, 146.06, 146.31, 152.76, 153.34.
EI-MS (70 eV): m/z (%): 1387,6682.
IR [cm−1]: (840, 916, 1008, 1176, 1184, 1244, 1256, 1320, 1480, 1700, 2968, 3512).
Anal. Calcd for C72H78N2O18S4: C, 62.32; H, 5.67; N, 2.09; S, 9.24.
Found: C, 62.27; H, 5.68; N, 2.13; S, 9.26.
General Procedure for the Synthesis of the Boron Derivatives from
bis-L-Proline-tetratosylresorcinarene (4a–e)
A solution of bis-l-prolinetetratosylresorcinarene 3a (0.7 mmol, 1.0 g) and corresponding
derivative of boric acid in MeCN (50 ml) was heated under refluxed for 5h. After evapo-
ration of the solvent, the residue was purified by crystallization from CHCl3 or by column
chromatography with acetone-hexane (2:3) as eluent.
Product of Reaction with B(OH)3 (4a), 90% yield, was purified by crystallization
from CHCl3, mp. >340◦C, [α]D25 = −205◦ (CHCl3, c 0.284).
1H NMR (500 MHz) CDCl3, 25◦C): δ 1.19 (d, J = 6.9Hz, 6H, -CH3), 1.46 (d, J =
6.9Hz, 6H, -CH3), 2.03 (m, 4H, H4 i H5), 2.25 (m, 2H, H3), 2.27 (m, 2H, H2), 2.43
(s, 6H, Ar-CH3), 2.51 (s, 6H, Ar-CH3), 2.80 (m, 2H, H6), 3.60 (d, J = 16.0Hz, 2H, H8),

Synthesis and Structure of Bora Derivatives of Resorcinarenes
223
3.79 (dd, J = 8.0,4.0Hz 2H, H1), 4.16 (d, J = 12.0Hz, 2H, H9), 4.21 (m, 2H, H7), 4.35 (q,
J = 6.9Hz, 2H, -CHCH3), 4.56 (q, J = 6.9Hz, 2H, -CHCH3), 6.29 (s, 2H, ArH), 6.56 (s,
2H, ArH), 7.10 (s, 2H, ArH), 7.41 (d, J = 6.9Hz, 4H, ArH), 7.50 (d, J = 6.9Hz, 4H, ArH),
7.90 (d, J = 6.9Hz, 4H, ArH), 8.06 (d, J = 6.9Hz, 4H, ArH).
13C NMR (500 MHz) CDCl3, 25◦C): δ 9.521, 20.943, 21.703, 21.856, 24.917, 29.102,
31.697, 32.459, 52.322, 59.077, 59.077, 69.109, 76.744, 76.999, 77.252, 108.269, 115.160,
119.233, 124.364, 125.927, 127.014, 128.357, 128.825, 130.128, 130.705, 130.897,
133.041, 138.171, 141.198, 144.417, 145.026, 145.714, 146.771, 150.223, 152.840,
171.906.
EI-MS (70 eV): m/z (%): 1467,2388.
IR [cm−1]: (684, 792, 848, 972, 1020, 1092, 1128, 1176, 1368, 1488, 1600, 1740,
2968, 3432).
Anal. Calcd for C72H72B2N2O22S4: C, 58.94; H, 4.95; N, 1.91; S, 8.74; B, 1.47.
Found: C, 59.09; H, 5.05; N, 1.98; S, 8.77; B, 1.49.
Product of Reaction with PhB(OH)2 (4b), 60% yield, was purified by crystallization
from CHCl3, mp. 218–219◦C, [α]D25 = −224◦ (CHCl3, c 0.208).
1H NMR (500 MHz) CDCl3, 25◦C): δ 1.13 (d, J = 6.5Hz, 6H, -CH3), 1.43 (d, J =
6.5Hz, 6H, -CH3), 1.82 (m, 2H, H5), 1.85 (m, 2H, H4), 2.26 (m, 2H, H3), 2.33 (s, 6H,
Ar-CH3), 2.37 (s, 6H, Ar-CH3), 2.43 (m, 2H, H2), 3.09 (m, 2H, H6), 3.58 (d, J = 13.5Hz,
2H, H8), 3.91 (dd, J = 9.0,3.5Hz, 2H, H1), 4.03 (m, 2H, H7), 4.13 (q, J = 6.5Hz, 2H,
-CHCH3), 4.26 (d, J = 13.5Hz, 2H, H9), 4.59 (q, J = 6.5Hz, 2H, -CHCH3), 6.06 (s, 2H,
ArH), 6.27 (s, 2H, ArH), 7.05 (s, 2H, ArH), 7.32 (d, J = 6.9Hz, 4H, ArH), 7.35 (d, J =
8.0Hz, 4H, ArH), 7.38 (d, J = 8.0Hz, 4H, ArH), 7.81 (d, J = 8.0Hz, 4H, ArH).
13C NMR (500 MHz) CDCl3, 25◦C): δ 18.955, 20.757, 21.717, 21.768, 23.527,
27.229, 32.055, 32.651, 49.735, 60.179, 66.251, 76.746, 77.000, 77.255, 105.795, 114.828,
117.946, 123.671, 126.223, 126.445, 127.699, 128.024, 128.140, 129.065, 129.963,
130.144, 130.429, 132.253, 133.715, 137.481, 140.514, 144.300, 145.115, 145.548,
146.371, 150.821, 153.010, 173.813.
EI-MS (70 eV): m/z (%): 1587,4360.
IR [cm−1]: (744, 798, 840, 932, 1160, 1152, 1184, 1324, 1420, 1536, 1556, 1684,
2960, 3120).
Anal. Calcd for C84H80B2N2O20S4: C, 63.56; H, 5.08; N, 1.76; S, 8.08; B, 1.36.
Found: C, 63.58; H, 5.12; N, 1.78; S, 8.13; B, 1.39.
Product of Reaction with 3-ClPhB(OH)2 (4c), 74% yield, was purified by column
chromatography with acetone-hexane (2:3), mp. 213–214◦C, [α]D25 = −271◦ (CHCl3,
c 0.164).
1H NMR (500 MHz) CDCl3, 25◦C): δ 1.20 (d, J = 6.9Hz, 6H, -CH3), 1.25 (m, 4H, H4
and H5), 1.50 (d, J = 6.9Hz, 6H, -CH3), 1.89 (m, 4H, H2 and H3), 2.40 (s, 6H, Ar-CH3),
2.44 (s, 6H, Ar-CH3), 2.50 (m, 2H, H6), 3.65 (d, J = 16.0Hz, 2H, H8), 3.98 (dd, J =
8.0,4.0Hz, 2H, H1), 4.20 (q, J = 6.9Hz, 4H, -CHCH3), 4.33 (d, J = 12.0Hz, 2H, H9), 4.52
(m, 2H, H7), 4.66 (q, J = 6.9Hz, 4H, -CHCH3), 6.11 (s, 2H, ArH), 6.34 (s, 2H, ArH), 6.77
(s, 2H, ArH), 7.41 (m, 10H, ArH), 7.89 (d, J = 6.9Hz, 4H, ArH).
13C NMR (500 MHz) CDCl3, 25◦C): δ 18.991, 20.688, 21.717, 21.724, 21.806, 23.699,
27.266, 32.084, 32.644, 49.943, 60.347, 66.377, 76.750, 77.004, 77.258, 106.021, 115.027,
118.461, 123.909, 126.383, 126.459, 128.116, 128.182, 128.984, 129.590, 129.959,

224
Iwanek et al.
130.136, 130.426, 130.477, 131.834, 133.693, 133.765, 137.463, 140.494, 144.296,
145.180, 145.472, 146.539, 150.820, 152.769, 173.372.
EI-MS (70 eV): m/z (%): 1656,3262.
IR [cm−1]: (604, 784, 844, 932, 1080, 1192, 1288, 1324, 1420, 1540, 1568, 1688,
2968, 3472).
Anal. Calcd for C84H78B2Cl2N2O20S4: C, 60.91; H, 4.75; N, 1.69; S, 7.74; B, 1.31; Cl,
4.28.
Found: C, 60.96; H, 4.77; N, 1.71; S, 7.76; B, 1.34; Cl, 4.29.
Product of Reaction with 3,5-Br2PhB(OH)2 (4d), 97% yield, was purified by col-
umn chromatography with acetone-hexane (2:3), mp. 235–236◦C, [α]D25 = −189◦ (CHCl3,
c 0.230).
1H NMR (500 MHz) CDCl3, 25◦C): δ 1.15 (d, J = 6.9Hz, 6H, -CH3), 1.49 (d, J =
6.9Hz, 6H, -CH3), 1.91 (m, 2H, H5), 2.05 (m, 2H, H4), 2.17 (s, 6H, Ar-CH3), 2.30 (m,
4H, H2 and H3), 2.45 (s, 6H, Ar-CH3), 2.74 (m, 2H, H6), 2.96 (m, 2H, H7), 3.76 (d, J =
16.0Hz, 2H, H8), 3.92 (dd, J = 8.0,4.0Hz, 2H, H1), 4.15 (q, J = 6.9Hz, 4H, -CHCH3),
4.57 (d, J = 12.0Hz, 2H, H9), 4.69 (q, J = 6.9Hz, 4H, -CHCH3), 6.11 (s, 2H, ArH), 6.28
(s, 2H, ArH), 6.76 (s, 2H, ArH), 7.05 (s, 2H, ArH), 7.13 (d, J = 6.9Hz, 4H, ArH), 7.37
(d, J = 6.9Hz, 4H, ArH), 7.44 (d, J = 6.9Hz, 4H, ArH), 7.61 (m, 2H, ArH), 7.67 (m, 2H,
ArH), 7.91 (d, J = 6.9Hz, 4H, ArH).
13C NMR (500 MHz) CDCl3, 25◦C): δ 18.750, 20.448, 21.721, 21.816, 24.140, 27.546,
30.913, 32.120, 32.575, 50.423, 60.723, 66.403, 76.744, 76.999, 77.252, 107.292, 115.527,
119.802, 123.001, 124.218, 126.544, 126.623, 128.116, 128.959, 129.794, 129.916,
130.540, 133.426, 133.591, 133.696, 137.467, 140.178, 144.353, 145.222, 146.676,
150.997, 152.531, 172.941.
EI-MS (70 eV): m/z (%): 1903,0204.
IR [cm−1]: (600, 788, 932, 960, 1080, 1136, 1192, 1272, 1324, 1420, 1556, 1672,
2960, 3016).
Anal. Calcd for C84H76B2Br4N2O20S4: C, 53.02; H, 4.03; N, 1.47; S, 6.74; B, 1.14;
Br, 16.79.
Found: C, 53.00; H, 4.10; N, 1.43; S, 6.79; B, 1.18; Br, 16.82.
Product of Reaction with B(OCH3)3 (4e), 65% yield, was purified by column chro-
matography with acetone-hexane (2:3), mp. 189–190◦C, [α]D25 = −103◦ (CHCl3, c 0.362).
1H NMR (500 MHz) CDCl3, 25◦C): δ 1.28 (d, J = 6.9Hz, 6H, -CH3), 1.49 (d, J =
6.9Hz, 6H, -CH3), 1.99 (m, 2H, H5), 2.10 (m, 2H, H4), 2.25 (m, 2H, H3), 2.25 (m, 2H, H2),
2.34 (s, 6H, Ar-CH3), 2.48 (s, 6H, Ar-CH3), 2.86 (m, 2H, H6), 3.21 (s, 6H, -OCH3), 3.45
(d, J = 14.9Hz, 2H, H8), 3.75 (dd, J = 8.0,4.0Hz, 2H, H1), 4.02 (m, 2H, H7), 4.20 (d, J =
14.9Hz, 2H, H9), 4.24 (q, J = 6.9Hz, 4H, -CHCH3), 4.51 (q, J = 6.9Hz, 4H, -CHCH3),
6.20 (s, 2H, ArH), 6.57 (s, 2H, ArH), 6.76 (s, 2H, ArH), 7.07 (s, 2H, ArH), 7.43 (d, J =
6.9Hz, 4H, ArH), 7.51 (d, J = 6.9Hz, 4H, ArH), 7.84 (d, J = 6.9Hz, 4H, ArH), 8.01 (d, J
= 6.9Hz, 4H, ArH).
13C NMR (100 MHz) CDCl3, 25◦C): δ 20.316, 20.453, 20.791, 21.221, 23.661, 24.109,
24.337, 24.712, 25.791, 28.249, 28.825, 29.017, 29.144, 29.291, 29.437, 29.602, 29.821,
30.360, 30.452, 32.124, 33.322, 36.219, 40.734, 46.172, 50.066, 52.003, 52.670, 55.833,
58.364, 58.566, 67.367, 68.354, 79.185, 100.489, 109.017, 109.346, 113.888, 114.044,
124.710, 124.874, 125.148, 127.817, 127.890, 128.027, 128.585, 128.896, 130.239,

Synthesis and Structure of Bora Derivatives of Resorcinarenes
225
130.404, 132.241, 132.241, 132.314, 132.479, 132.762, 138.026, 138.282, 143.510,
143.793, 145.375, 145.695, 145.877, 149.954, 151.453, 151.855, 171.879, 172.127.
EI-MS (70 eV): m/z (%): 1497,3082.
IR [cm−1]: (668, 760, 836, 992, 1072, 1192, 1224, 1324, 1372, 1484, 1600, 1748,
2968, 3080).
Anal. Calcd for C74H78B2N2O22S4: C, 59.36; H, 5.25; N, 1.87; S, 8.57; B, 1.44.
Found: C, 59.33; H, 5.23; N, 1.89; S, 8.55; B, 1.48.
General Procedure for the Synthesis of the Boron Derivatives from
bis-L-Prolinol-tetratosylresorcinarene (4f–h)
A mixture of bis-l-prolinoltetratosyloresorcinarene 3b (0.7 mmol, 0.97 g) and phenylboric
acid (1.5 mmol) or its derivatives in toluene (50 ml) heated for 5h at 140◦C with azeotropic
socket. After evaporation of the solvent the residue was purified by column chromatography
with acetone-hexane (2:3) as eluent.
Product of Reaction with PhB(OH)2 (4f), 61% yield, mp. 295–296◦C, [α]D25 = +121◦
(CHCl3, c 0.234).
1H NMR (500 MHz) CDCl3, 25◦C): δ 1.25 (d, J = 6.9Hz, 6H, -CH3), 1.42 (d, J =
6.9Hz, 6H, -CH3), 1.46 (m, 2H, H5), 1.51 (m, 2H, H4), 2.05 (m, 2H, H4), 2.16 (s, 6H, Ar-
CH3), 2.21 (s, 6H, Ar-CH3), 2.44 (m, 2H, H2), 3.19 (m, 2H, H6), 3.35 (dd, J = 9.0,4.5Hz,
2H, H7), 3.41 (m, 2H, H1), 3.74 (d, J = 15.5Hz, 2H, H8), 4.05 (d, J = 15.5Hz, 2H, H9),
4.31 (dd, J = 14.5,7.0Hz, 2H, HA), 4.44 (dd, J = 14.5,7.0Hz, 2H, HB), 4.51 (q, J = 7.0Hz,
4H, -CHCH3), 4.58 (q, J = 7.0Hz, 4H, -CHCH3), 6.20 (s, 2H, ArH), 6.36 (s, 2H, ArH),
6.47 (d, J = 7.0Hz, 4H, ArH), 6.58 (d, J = 7.0Hz, 4H, ArH), 6.60 (s, 2H, ArH), 7.06 (s,
2H, ArH), 7.15 (s, 2H, ArH), 7.32 (d, J = 7.0Hz, 4H, ArH), 7.45 (m, 4H, ArH), 7.61 (d, J
= 7.0Hz, 2H, ArH), 7.87 (d, J = 7.0Hz, 4H, ArH).
13C NMR (500 MHz) CDCl3, 25◦C): δ 19.755, 20.857, 21.712, 21.759, 21.762, 22.878,
23.631, 26.889, 27.342, 30.921, 31.542, 32.055, 32.302, 32.653, 49.732, 60.279, 66.168,
76.744, 76.997, 77.256, 103.584, 107.792, 115.148, 117.926, 122.674, 126.893, 127.695,
128.124, 128.540, 128.673, 129.165, 129.183, 130.101, 130.229, 130.456, 130.621,
132.893, 133.915, 137.581, 144.728, 145.515, 145.858, 146.471, 150.182, 153.042.
EI-MS (70 eV): m/z (%): 1559,4696.
IR [cm−1]: (744, 798, 840, 932, 1160, 1152, 1184, 1324, 1420, 1536, 1556, 1684,
2960, 3120).
Anal. Calcd for C84H84B2N2O18S4: C, 64.70; H, 5.43; N, 1.80; S, 8.22; B, 1.39.
Found: C, 64.68; H, 5.46; N, 1.83; S, 8.26; B, 1.35.
Product of Reaction with 3-ClPhB(OH)2 (4g), 53% yield, mp. 267–268◦C, [α]D25
+135◦ (CHCl3, c 0.276).
=
1H NMR (500 MHz) CDCl3, 25◦C): δ 1.34 (d, J = 6.9Hz, 6H, -CH3), 1.47 (d, J =
6.9Hz, 6H, -CH3), 1.93 (m, 2H, H5), 2.01 (m, 2H, H4), 2.15 (s, 6H, Ar-CH3), 2.19 (m, 2H,
H3), 2.27 (s, 6H, Ar-CH3), 2.37 (m, 2H, H2), 3.05 (m, 2H, H1), 3.32 (m, 4H, H6 and H7),
3.70 (d, J = 15.5Hz, 2H, H8), 4.06 (d, J = 15.5Hz, 2H, H9), 4.33 (dd, J = 14.5,6.8Hz,
2H, HA), 4.46 (dd, J = 14.5,6.8Hz, 2H, HB), 4.52 (q, J = 6.9Hz, 4H, -CHCH3), 4.57 (q,
J = 6.9Hz, 4H, -CHCH3), 6.18 (s, 2H, ArH), 6.45 (s, 2H, ArH), 6.51 (d, J = 7.0Hz, 2H,
ArH), 6.74 (s, 2H, ArH), 6.78 (d, J = 7.0Hz, 4H, ArH), 7.07 (s, 2H, ArH), 7.16 (s, 2H,

226
Iwanek et al.
ArH), 7.13 (s, 2H, ArH), 7.06 (s, 2H, ArH), 7.45 (m, 4H, ArH), 7.64 (d, J = 7.0Hz, 2H,
ArH), 7.89 (d, J = 7.0Hz, 4H, ArH).
13C NMR (100 MHz) CDCl3, 25◦C): δ 19.197, 19.611, 20.151, 21.761, 21.799, 21.838,
21.869, 22.752, 25.623, 30.691, 30.918, 31.970, 32.266, 32.486, 32.861, 59.809, 67.809,
76.744, 76.999, 77.252, 103.631, 107.050, 115.034, 115.919, 120.045, 126.949, 128.161,
128.560, 128.681, 129.178, 130.069, 130.209, 130.412, 130.503, 130.674, 132.940,
133.919, 137.579, 144.737, 145.669, 145.805, 146.044, 146.534, 153.188.
EI-MS (70 eV): m/z (%): 1628,3598.
IR [cm−1]: (664, 696, 844, 976, 1084, 1176, 1192, 1272, 1360, 1480, 1596, 2976,
3488).
Anal. Calcd for C84H82B2Cl2N2O18S4: C, 61.96; H, 5.08; N, 1.72; S, 7.88; B, 1.33; Cl,
4.35.
Found: C, 62.03; H, 5.14; N, 1.71; S, 7.92; B, 1.35; Cl, 4.36.
Product of Reaction with 3,5-Br2PhB(OH)2 (4h), 78% yield, mp. 282–283◦C, [α]D25
= +106◦ (CHCl3, c 0.228).
1H NMR (500 MHz) CDCl3, 25◦C): δ 1.27 (d, J = 6.9Hz, 6H, -CH3), 1.50 (d, J =
6.9Hz, 6H, -CH3), 1.95 (m, 2H, H5), 1.99 (m, 2H, H4), 2.16 (m, 2H, H3), 2.35 (s, 6H,
Ar-CH3), 2.47 (s, 6H, Ar-CH3), 2.91 (m, 2H, H2), 3.01 (m, 2H, H6), 3.22 (m, 2H, H7),
3.28 (dd, J = 9.0,4.5Hz 2H, H1), 3.69 (d, J = 15.5Hz, 2H, H8), 4.08 (d, J = 15.5Hz, 2H,
H9), 4.33 (dd, J = 14.5,7.0Hz, 2H, HA), 4.45 (dd, J = 14.5,7.0Hz, 2H, HB), 4.53 (q, J =
7.0Hz, 4H, -CHCH3), 4.56 (q, J = 7.0Hz, 4H, -CHCH3), 6.20 (s, 2H, ArH), 6.36 (s, 2H,
ArH), 6.47 (d, J = 7.0Hz, 4H, ArH), 6.58 (d, J = 7.0Hz, 4H, ArH), 6.60 (s, 2H, ArH),
7.06 (s, 2H, ArH), 7.13 (s, 2H, ArH), 7.06 (s, 2H, ArH), 7.45 (m, 4H, ArH), 7.64 (d, J =
7.0Hz, 2H, ArH), 7.89 (d, J = 7.0Hz, 4H, ArH).
13C NMR (500 MHz) CDCl3, 25◦C): δ 19.298, 19.702, 20.299, 20.607, 21.663, 21.862,
22.983, 23.392, 25.273, 26.875, 29.665, 31.424, 31.985, 32.299, 32.540, 32.883, 34.627,
66.139, 68.031, 68.974, 76.747, 77.001, 77.255, 103.582, 103.950, 107.086, 115.247,
117.970, 122.735, 126.953, 127.671, 128.192, 128.336, 128.501, 128.611, 128.841,
129.563, 130.108, 130.270, 130.374, 130.471, 130.550, 130.619, 135.535, 135.756,
145.708, 146.588, 154.049.
EI-MS (70 eV): m/z (%): 1875,0540.
IR [cm−1]: (552, 664, 840, 976, 1072, 1176, 1192, 1288, 1368, 1484, 1540, 1596,
2968, 3008).
Anal. Calcd for C84H80B2Br4N2O18S4: C, 53.81; H, 4.30; N, 1.49; S, 6.84; B, 1.15;
Br, 17.05.
Found: C, 53.79; H, 4.34; N, 1.53; S, 6.82; B, 1.18; Br, 17.08.
Acknowledgements
The authors gratefully acknowledge the financial support from DAAD (German Academic
Exchange Service) for the Polish-German cooperation.
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