Synthesis, characterization and reactions of enantiomerically pure 'winged' spirane porphyrazines

Article abstract of DOI:10.1016/S0040-4020(00)00607-4

A series of enantiomerically pure porphyrazineoctaol derivatives have been prepared from L-(+)-dimethyl tartrate via conversion into the corresponding dispoke protected dihydroxymaleonitrile, Linstead macrocyclization and transmetallation. The derived chloromanganese(III) complexes catalyzed the epoxidation of styrene with sodium hypochlorite as the oxygen atom source but with modest enantioselectivities (<25%). (C) 2000 Elsevier Science Ltd. All rights reserved.

Full text of DOI:10.1016/S0040-4020(00)00607-4

TETRAHEDRON
Pergamon
Tetrahedron 56 (2000) 6565±6569
Synthesis, Characterization and Reactions of Enantiomerically
Pure `Winged' Spirane Porphyrazines
Shun-ichiro Hachiya,a Andrew S. Cook,a D. Bradley G. Williams,a Antonio Garrido Montalban,a
b,
Anthony G. M. Barretta, and Brian M. Hoffman
*
*
aDepartment of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington, London SW7 2AY, UK
bDepartment of Chemistry, Northwestern University, Evanston, IL 60208, USA
Received 20 April 2000; revised 13 June 2000; accepted 29 June 2000
AbstractÐA series of enantiomerically pure porphyrazineoctaol derivatives have been prepared from l-(1)-dimethyl tartrate via
conversion into the corresponding dispoke protected dihydroxymaleonitrile, Linstead macrocyclization and transmetallation. The derived
chloromanganese(III) complexes catalyzed the epoxidation of styrene with sodium hypochlorite as the oxygen atom source but with modest
enantioselectivities (,25%). q 2000 Elsevier Science Ltd. All rights reserved.
Porphyrinic macrocycles are the subject of great interest in
areas such as catalysis,1 photodynamic therapy,2 and in the
fabrication of molecular electronic3 or magnetic devices.4
Our efforts in this area utilize the tetraazaporphyrin
(porphyrazine, pz) ligand, and we have published exten-
sively on the synthesis of diverse porphyrazines bearing 2,
4, 6 and 8 thio-5±7 or amino8 groups as peripheral macro-
cyclic ring substituents. More recently we described the ®rst
synthesis of porphyrazinoctaol derivatives in enantio-
merically pure form via a simple, reliable strategy based
on the Ley dispoke protection procedure.9 Indeed, the
development of oxidation reactions in which chiral metal-
loporphyrins are used as catalysts has received increased
attention over the past two decades.10 Herein we report
full experimental data on the synthesis of porphyrazine-
octaols 6a, 6b, 7a, 7b, 8a and 8b and a study of the
epoxidation of styrene using the chloromanganese(III)
complexes 8a and 8b as catalysts and sodium hypochlorite
as the oxygen atom source.
hydrogen chloride14 gave the dispiroketals 3a and 3b in
60 and 69% yield, respectively (Scheme 1). In consequence
of the double anomeric effect, only one diastereoisomer of
each 3a and 3b was formed under conditions of thermo-
dynamic control.15 In addition, the chirality inherent in the
tartrate controlled the spirane stereochemistry and resulted
Results and Discussion
The two chiral 2,3-dihydroxymaleonitrile precursors 5a11
and 5b, employed in this study, were synthesized starting
from dimethyl tartrate and using a Ley dispoke protection
strategy.12±14 Thus, reaction of excess l-(1)-dimethyl
tartrate (1) with both 3,30,4,40-tetrahydro-6,60-bi-2H-pyran
(2a)12 and (2R,20R) 2,20-diphenyl-3,30,4,40-tetrahydro-6,60-
bi-2H-pyran (2b)13 in diethyl ether in the presence of
Keywords: porphyrins and analogs; complexes; epoxidation; asymmetric
induction.
* Corresponding authors. Tel.: 1207-594-5766; fax: 1207-594-5805;
e-mail: agmb@ic.ac.uk
Scheme 1.
0040±4020/00/$ - see front matter q 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4020(00)00607-4

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S. Hachiya et al. / Tetrahedron 56 (2000) 6565±6569
Scheme 2.
Figure 1. UV±Vis spectra of porphyrazines 6a, 7a and 8b in CHCl3.
in products in which the methoxycarbonyl moieties are
equatorial. Monoiodination of 3a and 3b, via reaction of
the corresponding enolates with iodine, followed by
dehydroiodination in situ afforded the chiral alkenes 4a
and 4b (53%). Amide formation using saturated ammonia
solutions (in methanol for 4a or in a 2:1 mixture of
methanol/tetrahydrofuran in which 4b is more soluble)
and dehydration with tri¯uoroacetic anhydride proceeded
smoothly to give dinitriles 5a and 5b in 77 and 95% overall
yields (Scheme 1). Subsequent Linstead16 macrocyclization
of 5a and 5b using magnesium propoxide in propanol
provided the magnesium porphyrazines 6a and 6b in 45
and 88% yield, respectively (Scheme 2). Demetallation
was cleanly achieved without epimerization at the spirane
centers by reaction with glacial acetic acid, thus providing
macrocycles 7a and 7b (79%). The structure of the D2-
symmetric, enantiomerically pure porphyrazine 7a was
con®rmed by X-ray analysis.9 Remetallation of the corre-
sponding free base porphyrazines 7a and 7b with
manganese(II) acetate in the presence of potassium
hydroxide and air, followed by exchange of the axial ligand
during workup, gave the requisite manganese(III) chloride
derivatives 8a and 8b in high yield (86%) (Scheme 2).
band and the n±pp transition are blue-shifted to 338 and
427 nm, respectively. Insertion of the Mn(III) into the
porphyrazine causes striking changes in the electronic
absorption spectrum, which are not amenable to simple
interpretation. Although 8b exhibits similar bands to those
of the Mg-derivative 6a in the Soret and Q regions, addi-
tional transitions which we tentatively assigned to LMCT
(Ligand to Metal Charge Transfer) absorbances of the type
a2u (ring)!eg, as suggested in analogous porphyrin
spectra,17,18 are observed.
In order to examine the enantioselective catalytic activity of
the chiral manganese(III) chloride complexes 8a and 8b,
epoxidations of styrene were carried out in buffered aqueous
sodium hypochlorite solutions (pH 10.5) since epoxidation
rates have been reported to be satisfactorily high and
concomitant ole®n chlorination low under these conditions
for related porphyrin analogs.19 Epoxidation of styrene in
the presence of both trioctylmethylammonium chloride, as
phase transfer catalyst, and porphyrazine 8a (3 mol %) gave
styrene oxide (82%, GC-MS). The enantiomeric excess (ee)
of the isolated styrene oxide (39%) was shown to be 12% by
proton NMR spectroscopy in the presence of the chiral shift
reagent Eu(hfc)3.20 In the case of metalloporphyrin
catalysts, addition of small amounts of nitrogen centered
ligands have often been found to give better chemical yields
and/or enantioselectivities.21 However, no improved yields
or enantioselectivities were observed for the 8a-catalyzed
reactions in the presence of pyridine. On the other hand,
epoxidation catalyzed by the more bulky chloromangane-
se(III) porphyrazine 8b gave styrene oxide (63% isolated
yield, 25% ee).
Representative electronic absorption spectra of compounds
6a, 7a and 8b are shown in Fig. 1. Porphyrazine 6a exhibits
a Q-band at 599 nm, a less intense band at 455 nm, and a
band in the Soret region at 347 nm. In agreement with other
peripherally heterosubstituted (S, N) porphyrazines,5,8 we
tentatively assigned the peak at 455 nm to the n±pp transi-
tion from the lone-pairs on the peripheral oxygen atoms into
a pp ring orbital. In contrast, the demetallated product 7a
exhibits a split Q-band having Qx and Qy absorbances at 554
and 632 nm, respectively. The splitting re¯ects the change
in symmetry (D4h!D2h) and can be rationalized by
Gouterman's four-orbital model.17 In addition, the Soret
The synthesis of a new family of chiral porphyrazineoctaol

S. Hachiya et al. / Tetrahedron 56 (2000) 6565±6569
6567
derivatives has been achieved successfully. Whilst the
chloromanganese(III) porphyrazines 8a and 8b were active
as catalysts for the epoxidation of styrene, the enantio-
selectivities were too low to be of signi®cance. However,
the use of the dispoke protection is to be commended for the
concise preparation of porphyrazinediols and related
electron rich porphyrazine systems. Further aspects of the
chemistry of such porphyrazines will be reported in due
course.
organic layers were washed with saturated Na2SO3
(3£25 mL), H2O (3£25 mL), brine (3£25 mL) and dried
(Na2SO4). Rotary evaporation and chromatography
(hexanes/CH2Cl2/EtOAc 22/10/1) followed by recrystalliza-
tion (EtOAc/CH2Cl2/hexanes) afforded alkene 4b (1.15 g,
53%) as a white crystalline solid: mp 1848C; Rf 0.45
(hexanes/CH2Cl2/EtOAc 22/10/1); [a]2D5ˆ2125.0 (cˆ
0.28, CHCl3); IR (neat) 1746, 1436, 1318, 1195, 1080,
1
970 cm21; H NMR (CDCl3, 300 MHz) d 1.59±1.70 (m,
2H), 1.83±2.05 (m, 6H), 2.20±2.33 (m, 4H), 3.82 (s, 6H),
4.97 (dd, Jˆ1.7, 11.7 Hz, 2H), 7.28±7.37 (m, 10H); 13C
NMR (CDCl3, 75 MHz) d 18.7, 27.6, 32.7, 52.5, 73.3,
98.0, 125.9, 127.4, 128.2, 130.6, 142.6, 163.1; MS (FAB)
495 (M1z); HRMS (FAB) calcd for C28H31O8: (M1H)1
495.2019, found: (M1H)1 495.2058. Anal. Calcd for
C28H30O8: C, 67.99; H, 6.12. Found: C, 67.87; H, 6.14.
Experimental
All reactions were conducted in oven or ¯ame dried glass-
ware. Reaction temperatures reported refer to external bath
temperatures. Hexanes refers to the petroleum fraction bp
40±608C. Solvents were distilled prior to use: THF and Et2O
(from Na/Ph2CO); CH2Cl2 (from CaH2); DMF [predried
over BaO, distilled from alumina (activity I)]; propanol
(from Mg); pyridine (from Zn). All other reagents were
used as commercially supplied. Dinitrile 5a was prepared
from diester 1 via the dispiroketals 3a and 4a as reported
elsewhere.11 TLC was carried out on E. Merck precoated
silica gel 60 F254 plates; compounds were visualized using
UV radiation (254 nm). Chromatography refers to ¯ash
chromatography on E. Merck silica gel 60, 40±60 mm
(eluants are given in parentheses).
(2R,6R,7R,9R)-2,9-Diphenyl-1,8,13,16-tetraoxadispiro-
[5.0.5.4]hexadec-14-ene-14,15-dinitrile (5b). Diester 4b
(1.23 g, 2.48 mmol) in MeOH and THF (2/1; 40 mL) was
saturated with NH3 at 08C and stirred at 208C for 96 h.
Rotary evaporation and chromatography (EtOAc) followed
by recrystallization (CH2Cl2) afforded the corresponding
diamide (1.2 g, 100%) as a white crystalline solid: mp
130±1358C; Rf 0 (Et2O/hexanes 1/1); [a]2D5ˆ2110.0
(cˆ0.22, CHCl3); IR (neat) 3474, 3200, 1675, 1594, 1172,
1
1067, 971 cm21; H NMR (CDCl3, 300 MHz) d 1.56±1.68
(m, 2H), 1.63±2.08 (m, 6H), 2.16±2.30 (m, 4H), 4.82 (d,
Jˆ11.7 Hz, 2H), 7.25±7.36 (m, 10H); 13C NMR (CDCl3,
75 MHz) d 19.0, 27.6, 33.0, 73.6, 97.1, 125.8, 127.5,
128.3, 132.3, 142.0, 146.4; MS (FAB) 465 (M1z); HRMS
(FAB) calcd for C26H29N2O6: (M1H)1 465.2026, found:
(M1H)1 465.2038. Tri¯uoroacetic anhydride (0.79 mL,
5.58 mmol) was added dropwise to the diamide in pyridine
(30 mL) at 2308C over 30 min under N2. The solution was
allowed to warm up to 208C over 2 h, when Et2O (100 mL)
was added. The mixture was neutralized with 3N HCl and
extracted with EtOAc (3£50 mL). The combined organic
layers were washed with H2O (3£25 mL), and brine
(3£25 mL) and dried (Na2SO4). Rotary evaporation and
chromatography (hexanes/CH2Cl2/EtOAc 22/10/1) gave
dinitrile 5b (0.94 g, 95%) as a white solid: mp 215±
2188C; Rf 0.65 (hexanes/CH2Cl2/EtOAc 22/10/1);
[a]2D5ˆ283.6 (cˆ0.56, CHCl3); IR (neat) 2230, 1633,
;
1H NMR (CDCl3,
300 MHz) d 1.63±1.70 (m, 2H), 1.84±2.30 (m, 10H),
4.81 (dd, Jˆ2.4, 11.7 Hz, 2H), 7.27±7.44 (m, 10H); 13C
NMR (CDCl3, 75 MHz) d 18.2, 27.4, 32.6, 74.7, 100.0,
111.6, 121.5, 125.7, 128.0, 128.5, 140.9; MS (CI) 446
(M1NH4)1; HRMS (CI) calcd for C26H28N3O4:
(M1NH4)1 446.2080, found: (M1NH4)1 446.2088. Anal.
Calcd for C26H24N2O4: C, 72.87; H, 5.65; N, 6.54. Found: C,
72.35; H, 5.64; N, 6.39.
(2R,6R,7R,9R,14R,15R)-Dimethyl 2,9-diphenyl-1,8,13, 16-
tetraoxadispiro-[5.0.5.4]hexadecane-14,15-dicarboxylate
(3b). HCl was bubbled through l-(1)-dimethyl tartrate
(13.0 g, 73.2 mmol) in Et2O (390 mL) for 40 min at 08C
when diene 2b13 (5.18 g, 16.3 mmol) in THF (30 mL) was
added and the mixture was allowed to warm up to 108C over
5 h. The mixture was neutralized with 10% NaOH,
extracted with EtOAc (3£100 mL) and the combined
organic layers were washed with saturated NaHCO3
(3£100 mL), H2O (3£50 mL), brine (3£50 mL) and dried
(Na2SO4). Rotary evaporation and chromatography
(CH2Cl2/Et2O 9/1) followed by recrystallization (EtOAc/
CH2Cl2) afforded diester 3b (6.0 g, 69%) as a white crystal-
line solid: mp 2128C; Rf 0.40 (Et2O/hexanes 1/1);
[a]2D5ˆ151.2 (cˆ0.66, CHCl3); IR (neat) 1747, 1454,
1
1047 cm21; H NMR (CDCl3, 300 MHz) d 1.46±2.16 (m,
1256, 1218, 1089, 1044 cm21
12H), 3.76 (s, 6H), 4.64 (s, 2H), 4.82 (dd, Jˆ2.3, 11.6 Hz,
2H), 7.26±7.43 (m, 10H); 13C NMR (CDCl3, 75 MHz) d
18.7, 27.9, 33.2, 52.4, 68.2, 72.4, 97.7, 125.9, 127.3,
128.3, 142.6, 168.7; MS (FAB) 497 (M1z); HRMS (CI)
calcd for C28H36NO8: (M1NH4)1 514.2441, found:
(M1NH4)1 514.2435. Anal. Calcd for C28H32O8: C,
67.71; H, 6.50. Found: C, 67.63; H, 6.48.
(2R,6R,7R,9R)-Dimethyl 2,9-diphenyl-1,8,13,16-tetraoxa-
dispiro-[5.0.5.4]hexadec-14-ene-14,15-dicarboxylate (4b).
Lithium 2,2,6,6-tetramethylpiperidide, prepared from
2,2,6,6-tetramethylpiperidine (2.39 mL, 14.2 mmol) in
THF (6.0 mL) and n-BuLi in hexane (2.5 M; 5.49 mL),
was added dropwise to diester 3b (2.20 g, 4.43 mmol) in
THF (15 mL) at 2788C over 20 min. After stirring at
2788C for 2 h, I2 (1.35 g, 5.31 mmol) in THF (11 mL)
was added and the mixture allowed to warm up to 208C
over 16 h. The solution was poured onto saturated NH4Cl
(50 mL) and extracted with Et2O (3£50 mL). The combined
Mg-Pz (6a). A mixture of propanol (3 mL), Mg (5 mg,
0.04 mmol), and I2 (one small crystal) was heated to re¯ux
for 12 h under N2. The suspension was cooled and dinitrile
5a11 (95 mg, 0.34 mmol) was added and the mixture further
heated at re¯ux for 4 h. The deep blue suspension was
allowed to cool, ®ltered (silica) and the solids washed
with MeOH. Rotary evaporation and chromatography
(CHCl3; CHCl3/MeOH 39/1) gave Mg-porphyrazine 6a
(44 mg, 45%) as a dark blue solid: mp .3308C; Rf 0.37

6568
S. Hachiya et al. / Tetrahedron 56 (2000) 6565±6569
(CH2Cl2/MeOH 15/1); IR (CHCl3) 1638, 1187, 1098,
973 cm21; UV±Vis (CHCl3) lmax (log e) 347 (4.79), 455
(3.77), 551 (3.94), 599 (4.62) nm; 1H NMR (CDCl3,
300 MHz) d 1.71±1.89 (m, 16H), 1.96±2.11 (m, 16H),
2.39±2.56 (m, 16H), 3.60±3.73 (m, 8H), 4.02±4.10 (m,
8H); 13C NMR (CDCl3, 75 MHz) d 18.4, 25.0, 28.9, 62.3,
99.3, 137.6, 146.4; MS (FAB) 1129 (M1H)1.
MnCl-Pz (8a). Mn(OAc)2´4H2O (50.6 mg, 0.21 mmol) and
KOH (13.2 mg, 0.24 mmol) were added to porphyrazine 7a
(0.11 g, 0.10 mmol) in DMF (3 mL) and the mixture was
heated at 1008C for 12 h. Brine (5 mL) was added, and the
mixture extracted with Et2O and CH2Cl2 (4/1, 3£30 mL).
The combined organic layers were washed with H2O
(3£20 mL) and brine (3£20 mL) and dried (Na2SO4).
Rotary evaporation and chromatography (CH2Cl2/Et2O
9/1; 19/1) gave Mn-porphyrazine 8a (106 mg, 86%) as a
dark green solid: Rf 0.26 (CH2Cl2/MeOH 19/1); IR (KBr)
1631, 1222, 1104, 1053, 970, 918, 876 cm21; UV±Vis
(CHCl3) lmax (log e) 272 (4.43), 330 (4.44), 386 (4.38),
450 (4.32), 497 (4.23), 635 (4.22) nm; MS (FAB) 1159
(M1H2Cl).1 Anal. Calcd for C56H64ClMnN8O16: C,
56.26; H, 5.40; N, 9.38. Found: C, 55.97; H, 5.17; N, 9.17.
2H-Pz (7a). AcOH (1 mL) and porphyrazine 6a (36 mg,
0.032 mmol) was stirred at 208C for 16 h, poured onto ice
and water (10 mL) and the resulting suspension brought to
pH 7 with 1 M NaOH. The precipitate was collected via
vacuum ®ltration, washed with water and chromatographed
(CHCl3) to give porphyrazine 7a (30 mg, 79%) as a blue
solid: mp .3008C (decomp.); Rf 0.65 (CH2Cl2/Et2O 4/1); IR
(CHCl3) 3313, 1662, 1619, 1216, 1185, 1103, 971, 894,
755 cm21; UV±Vis (CHCl3) lmax (log e) 338 (4.20), 427
(3.68), 554 (3.75), 632 (3.83) nm; 1H NMR (CDCl3,
300 MHz) d 23.51 (br s, 2H), 1.77±1.90 (m, 16H), 2.09
(d, Jˆ12.8 Hz, 8H), 2.21 (dd, Jˆ13.2, 4.5 Hz, 8H), 2.62 (d,
Jˆ13.3 Hz, 8H) 2.76 (dd, Jˆ12.0, 4.1 Hz, 8H), 3.72 (d,
Jˆ9.5 Hz, 8H), 4.27 (td, Jˆ10.8, 4.7 Hz, 8H); 13C NMR
(CDCl3, 75 MHz) d 18.3, 24.9, 28.9, 62.5, 100.1, 137.6,
143.3; MS (FAB) 1107 (M1H)1; HRMS (FAB) calcd for
C56H67N8O16: (M1H)1 1107.4675, found: (M1H)1
1107.4706. An X-ray crystallography determination for 7a
has already been reported,9 CCDC-100184.
MnCl-Pz (8b). The same reaction conditions as above, but
at 1208C and 3 h, gave Mn-porphyrazine 8b (0.45 g, 86%)
after chromatography (CH2Cl2/EtOAc 9/1) as a dark green
solid: Rf 0.16 (CH2Cl2/EtOAc 9/1); IR (neat) 2951, 1631,
1227, 1051, 936, 863 cm21; UV±Vis (CHCl3) lmax (log e)
230 (4.32), 330 (4.45), 388 (4.41), 448 (4.34), 491 (4.23),
633 (4.28) nm; MS (FAB) 1768 (M±H±Cl)1. Anal. Calcd
for C104H96ClMnN8O16.H2O: C, 68.55; H, 5.42; N, 6.15.
Found: C, 68.58; H, 5.51; N, 6.05.
General procedure for the epoxidation of styrene with
NaOCl
2H-Pz (7b). Propanol (15 mL), Mg (26.8 mg, 1.1 mmol)
and I2 (one small crystal) were heated to re¯ux for 12 h
under N2. The suspension was cooled and dinitrile 5b
(0.82 g, 1.92 mmol) was added and the mixture further
heated at re¯ux for 24 h. The deep blue suspension was
allowed to cool, ®ltered (Celite) and the solids washed
with CH2Cl2. Rotary evaporation and chromatography
(hexanes/CH2Cl2/EtOAc 22/10/1) gave Mg-porphyrazine
6b (0.73 g, 88%) as a dark blue solid: Rf 0.30 (hexanes/
CH2Cl2/EtOAc 22/10/1); IR (neat) 1638, 1212, 1095,
Aqueous Na2HPO4 (0.05 M; 60 mL) was added to aqueous
NaOCl (1.6 M; 20 mL) and the pH adjusted to 10.5 with
3 M HCl. An aliquot (5 mL) of this solution was added to
the porphyrazine catalyst (0.015 mmol), styrene (52 mg,
0.5 mmol), dodecane (42.6 mg, 0.25 mmol) as the internal
standard, and trioctylmethylammonium chloride (101 mg,
0.5 mmol) in CH2Cl2 (2 mL) at 08C and the mixture was
allowed to warm up to 208C. Aliquots were removed at
intervals and the formation of the styrene oxide monitored
by GC-MS. After stirring for 3 h, the mixture was extracted
with Et2O (3£20 mL) and the combined organic layers
washed with H2O (3£50 mL), brine (3£50 mL) and dried
(Na2SO4). Rotary evaporation and chromatography
(hexanes/Et2O 19:1) gave styrene oxide of which the enan-
1
969 cm21; H NMR (CDCl3, 300 MHz) d 1.72±1.90 (m,
8H), 2.16±2.25 (m, 16H), 2.30±2.44 (m, 8H) 2.80±2.93
(m, 8H), 2.93±3.14 (m, 8H), 5.39 (br d, Jˆ11.3 Hz, 8H),
7.02±7.17 (m, 40H); 13C NMR (CDCl3, 75 MHz) d 19.0,
29.0, 33.5, 73.4, 100.5, 125.9, 127.0, 127.9, 137.9, 142.6,
146.3; MS (FAB) 1738 (M1z). Porphyrazine 6b and AcOH
(20 mL) in CH2Cl2 (20 mL) were stirred at 208C for 72 h.
The solution was diluted with Et2O (50 mL), brought to pH
7.0±7.5 with 1 M NaOH and the organic layer was sepa-
rated, washed with saturated NH4Cl (3£30 mL), H2O
(3£30 mL), brine (3£25 mL) and dried (Na2SO4). Rotary
evaporation and chromatography (hexanes/CH2Cl2/EtOAc
22/10/1) gave porphyrazine 7b (0.46 g, 79%) as a blue
solid: Rf 0.28 (hexanes/CH2Cl2/EtOAc 22/10/1); IR (neat)
3309, 1665, 1621, 1504, 1453, 1264, 1216, 1162, 1096,
1048, 987, 873, 732 cm21; UV±Vis (CHCl3) lmax (log e)
338 (4.89), 429 (4.37), 553 (4.45), 632 (4.55) nm; 1H NMR
(CDCl3, 300 MHz) d 1.80±1.97 (m, 8H), 2.19±2.27 (m,
16H), 2.32±2.47 (m, 8H), 2.84±2.93 (m, 8H), 2.96±3.10,
(m, 8H), 5.38 (br d, Jˆ10.5 Hz, 8H), 7.05±7.10 (m, 24H),
7.16±7.19 (m, 16H); 13C NMR (CDCl3, 75 MHz) d 19.0,
28.9, 33.1, 73.7, 100.9, 126.1, 127.2, 128.0, 137.4, 142.1,
145.0; MS (FAB) 1718 (M12H)1. Anal. Calcd for
C104H98N8O16´H2O: C, 72.03; H, 5.81; N, 6.46. Found: C,
71.93; H, 5.81; N, 6.25.
1
tiomeric excess was determined by H NMR spectroscopy
in the presence of Eu(hfc)3 as the chiral shift reagent.20
Acknowledgements
We thank the Glaxo Group Research Ltd. for the generous
endowment (A. G. M. B.), the Wolfson Foundation for
establishing the Wolfson Centre for Organic Chemistry in
Medicinal Science at Imperial College, the Engineering and
Physical Sciences Research Council, the National Science
Foundation and NATO for generous support of our studies.
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