Synthesis and characterization of a protected amino alcohol containing ortho-carborane

Article abstract of DOI:10.1016/S0277-5387(98)00121-1

The reaction between the alkyne, N- (5-Benzyloxy-2-pentynyl) phthalimide and decaborane (14) in the presence of dimethyl sulfide resulted in the isolation of 1-C₆H₄ (CO) ₂NCH₂-2-C₆H₅CH₂OCH ₂CH₂-1, 2-C₂B₁₀H₁₀ (5) , 1-methylphthalimido-2-ethylbenzyl ether-o-carborane, in moderate yield. Compound 5 was characterized by single crystal X-ray diffraction study. Compound 5 crystallizes in the P1 space group, a=10.5328 (5) A, b=11.9209 (6) A, c=10.3451 (3) A, α=110.492 (3) °, β=102.868 (3) °, γ=87.279 (2) °, Z=2, D_calc=1.226 gcm³, R=0.0491 for 3521 reflections with F>4.0σ. Deprotection of the ether linkage of 5 results in the formation of 1-C₆H₄ (CO) ₂NCH₂-2-HOCH₂CH₂-1, 2-C₂B₁₀H₁₀ (6) , 1-methylphthalimido-2-ethylalcohol-o-carborane. The transformation is accomplished by hydrogenation of (5) over a PdC catalyst and resulted in the efficient conversion of (5) into (6) (83% yield) . Experimental details and analytical data leading to the identification of the reported compounds is provided.

Full text of DOI:10.1016/S0277-5387(98)00121-1

Polyhedron Vol[ 06\ No[ 08\ pp[ 2280Ð2396\ 0887
Þ 0887 Elsevier Science Ltd
Pergamon
All rights reserved[ Printed in Great Britain
9166Ð4276:87 ,08[99¦9[99
\
PII] S9166Ð4276"87#99010Ð0
Synthesis and characterization of a protected
amino alcohol containing ortho!carborane
Ye Wu\a Patrick J[ Carrollb and William Quintanaa\ꢀ
a Department of Chemistry and Biochemistry\ New Mexico State University\ Box 29990\ Dept[ 2C\
Las Cruces\ NM 77992!7990\ U[S[A[
b Department of Chemistry and Laboratory for Research on the Structure of Matter\
University of Pennsylvania\ Philadelphia\ Pennsylvania\ 08093!5212\ U[S[A[
"Received 01 December 0886^ accepted 05 March 0887#
Abstract*The reaction between the alkyne\ N!"4!Benzyloxy!1!pentynyl#phthalimide and decaborane "03# in
the presence of dimethyl sul_de resulted in the isolation of 0!C5H3"CO#1NCH1!1!C5H4CH1OCH1CH1!0\ 1!
C1B09H09 "4#\ 0!methylphthalimido!1!ethylbenzyl ether!o!carborane\ in moderate yield[ Compound 4 was
¹
characterized by single crystal X!ray di}raction study[ Compound 4 crystallizes in the P0 space group\
Ä
Ä
Ä
aꢁ09[4217 "4# A\ bꢁ00[8198 "5# A\ cꢁ09[2340 "2# A\ aꢁ009[381 "2#>\ bꢁ091[757 "2#>\ gꢁ76[168 "1#>\ Zꢁ1\
Dcalcꢁ0[115 g:cm2\ Rꢁ9[9380 for 2410 re~ections with F×3[9s[ Deprotection of the ether linkage of 4 results
in the formation of 0!C5H3"CO#1NCH1!1!HOCH1CH1!0\ 1!C1B09H09 "5#\ 0!methylphthalimido!1!ethylalcohol!
o!carborane[ The transformation is accomplished by hydrogenation of "4# over a Pd:C catalyst and resulted
in the e.cient conversion of "4# into "5# "72) yield#[ Experimental details and analytical data leading to the
identi_cation of the reported compounds is provided[ Þ 0887 Elsevier Science Ltd[ All rights reserved
Keywords] carborane^ synthesis^ amino^ alcohol^ reactivity^ crystallography[
———————————————————————————————————————————————
INTRODUCTION
as a viable option for the treatment of certain tumors\
speci_cally malignant melanoma and glioblastoma
multiforme\ there are too few compounds that are
su.ciently selective to perform this task[ The two
compounds currently under clinical trials\
Na1B01H00SH "BSH# and boronophenylalanine
"BPA# exhibit a tumor to normal brain ratio of 0[58]0
and 2]0 respectively ð00\ 01Ł[ Another problem is the
low solubility of these compounds at physiological
pH\ this is especially true for BPA[ Therefore\ syn!
thetic methodology for the synthesis of bifunctional
carboranes is highly desirable[
The introduction of bifunctional alkynes into the
decaborane "03# framework to produce hetero!
bifunctional o!carboranes is not unprecedented in the
literature ð3Ð09\ 02\ 03Ł[ This methodology is simple
and e.cient[ The main obstacle is choosing the appro!
priate bifunctional alkyne needed to perform the reac!
tion[ Our objective was to _nd the appropriate alkyne
containing a protected amine and a protected alcohol
precursor that could be reacted with decaborane "03#[
Given the fact that this type of compound is not com!
mercially available\ one of the tasks for this study
The recent report by Hawthorne and coworkers and
that of Kahl and Kasar regarding the high!yield syn!
thesis of polyhedral carborane amino acids are sig!
ni_cant steps in the _eld of boron neutron capture
therapy ð0Ð2Ł[ There is de_nitely a need for the syn!
thesis and characterization of a wide variety of these
compounds if progress is to be made in this _eld[
Our approach relies in the introduction of a protected
amine and a protected alcohol into the carborane
cage\ using the well established synthetic route for the
preparation of substituted ortho!carboranes\ relying
on the reaction of an alkyne with decaborane "03# ð3Ð
09Ł[
The scope of the presented work is the synthesis of
compounds that might be suitable for use in boron
neutron capture therapy "BNCT#[ Although in recent
years there is an apparent acceptance of this technique
ꢀ Author to whom correspondence should be addressed[
Fax] 990 494 535 1538[
2280

2281
Y[ Wu et al[
was the synthesis of such a compound[ We chose chemical shifts were referenced to TMSꢁ9[99 ppm
C5H3"CO#1NCH1C2CCH1CH1OC5H4 as our pre! with positive values indicating down_eld shifts[ Infra!
cursor\ since it contained a protected amine and a red spectra were recorded on a Perkin!Elmer 226 grat!
protected alcohol[ In this communication we describe ing infrared spectrophotometer and on Perkin Elmer
the synthesis of this alkyne from its precursors and its 0619 Fourier transform spectrophotometer[ Low res!
subsequent transformation to the heterobifunctional olution mass spectrometry data was obtained in a HP
ortho!carborane[ The synthesis of this carborane GC:MS system\ model 4884[
could open the door for the preparation of other
bifunctional carboranes needed for BNCT[ The key
to successful BNCT is the delivery of 09B!containing
compounds to the malignant tumor cell selectively[
The necessary tumor:normal tissue and tumor:blood
ratios must be at least two ð04\ 05Ł[
X!ray crystallo`raphy
X!ray intensity data were collected on a Rigaku R!
AXIS IIc area detector employing graphite!mon!
ochromated Mo!Ka radiation "lꢁ9[60958 A# at a
Common strategies used to achieve the above indi!
cated objective include the attachment of boron con!
taining residues to existing compounds known to
accumulate in tumor tissues ð06Ł and to a variety of
recognition elements\ such as amino acids ð07\ 08Ł\
peptides ð04Ł\ antibodies ð19Ł\ nucleosides ð10Ð13Ł\
liposomes ð14Ł and other regulatory biomolecules ð15Ł[
The most commonly used boron containing residues
are carborane clusters\ such as ortho!carborane and
derivatives[ These clusters have the advantage over
monoboronated compounds\ since they contain up to
ten boron atoms and naturally abundant 09B may be
used ð16Ł[ Also these clusters are stable at physio!
logical pH[ The main task is the design and com!
bination of the boron clusters with the recognition
elements or derivative thereof[ This communication
intends to address this strategy[
Ä
temperature of 112 K for compound 4[ Indexing was
performed from a series of 0> oscillations with
exposures of 7 minutes per frame[ A hemisphere of
data was collected using 5> oscillations with exposures
of 3 minutes per frame[ The crystal to detector dis!
tance was 71 mm[ Oscillation images were processed
using bioteX ð18Ł\ producing a listing of unaveraged
F1 and s"F1# values which were then passed to the
teXsan ð29Ł program package for further processing
and structure solution on a Silicon Graphics Indigo
R3999 computer[ A total of 8099 re~ections were
measured over the ranges] 4[07¾1u¾49[69>\ −01¾
h¾01\ −03¾k¾01\ −01¾l¾01\ yielding 2838
unique re~ections "Rintꢁ9[9065#[ Other relevant crys!
tallographic data are given in Table 0[ The intensity
data were corrected for Lorentz and polarization
e}ects but not for absorption[
The structure was solved by direct methods "SIR81#
ð20Ł[ The re_nement was full!matrix least squares
based on F1 using SHELXL!82 ð21Ł[ All re~ections
were used during re_nement "F1|s that were exper!
imentally negative were replaced by F1ꢁ9#[ The
weighting scheme was wꢁ0:ðs1"Fo1#¦9[9475P1¦
9[2284PŁ where Pꢀ"F1o¦1Fc1#:2[
EXPERIMENTAL
All manipulations were carried out using standard
high vacuum or inert atmosphere techniques\ when
warranted\ as described by Shriver ð17Ł[
Materials
Non!hydrogen atoms were re_ned anisotropically^
cage hydrogens were re_ned isotropically^ all other
hydrogen atoms were re_ned using a {riding| model
which the positions of the hydrogen atoms were re!
idealized before each least squares cycle by applying
the coordinate shifts of the atom to which each hydro!
gen atom is attached[ Re_nement converged to
R0ꢁ9[9380 and wR1ꢁ9[0104 for 2410 re~ections for
which F×3s"F# and R0ꢁ9[9445\ wR1ꢁ9[0169 and
GOFꢁ0[969 for all 2838 unique\ non!zero re~ections
and 237 variables[ The maximum D:s in the _nal cycle
of least squares was 9[999 and the two most prominent
2!butynyl!0!ol\ benzyl bromide\ sodium hydride\
tetrahydrofuran\ dimethylformamide\ paraformal!
dehyde\ n!butyllithium "1[9 M in cyclohexane#\ mag!
nesium sulfate\ chloroform\ acetonitrile\ methanol\
ethanol\ potassium phthalimide\ hexanes\ silica gel\
acetone!d5\ CD2CN and CDCl2 were purchased form
Aldrich[ All solvents were dried prior to use[ Deca!
borane "03# was obtained from Strem Chemicals[
Physical measurements
peaks in the _nal Fourier were ¦9[080 and
2
Ä
−9[065 e:A [
The 017[3 MHz boron!00 and 399[9 MHz proton
spectra were obtained on a Varian Unity!399 Fourier
transform spectrometer[ All boron!00 chemical shifts
were referenced to BF2=O"C1H4#1ꢁ9[9 ppm with a
Selected bond distances and angles are given in
Table 1 and Table 2 respectively[ Final atomic pos!
itions for non Hydrogen atoms and their isotropic
negative sign indicating an up_eld shift[ Proton NMR parameters\ Hydrogen atom coordinates and dis!
at 199 MHz and carbon!02 NMR at 49[9 MHz were placement parameters\ non!hydrogen atom thermal
obtained on Varian Gemini!199 Fourier transform parameters\ full listing of interatomic distances and
spectrometer[ Proton chemical shifts and carbon!02 bond angles are available as supplementary material[

Synthesis and characterization of a protected amino alcohol containing ortho!carborane
2282
Table 0[ Summary of Structure Determination of 0!C5H3"CO#1NCH1!1!C5H4CH1
OCH1CH1!0\ 1!C1B09H09 "4#
Formula]
C19B09H16NO2
Formula weight]
326[43
Crystal class]
Space group]
triclinic
¹
P0 "è1#
Z
1
Cell constants]
a
b
c
Ä
09[4217"4# A
Ä
00[8198"5# A
Ä
09[2340"2# A
a
009[381"2#>
091[757"2#>
76[168"1#>
b
g
2
Ä
V
m
0074[41"8# A
9[61 cm−0
crystal size\ mm
Dcalc
F"999#
9[49×9[24×9[11
0[115 g:cm2
345
Ä
Radiation]
Mo!Ka "lꢁ9[60958 A#
1u range
4[07Ð49[69>
hkl collected]
−01¾h¾01^ −03¾k¾01^ −01¾l¾01
No[ re~ections measured]
No[ unique re~ections]
No[ observed re~ections
No[ re~ections used in re_nement
No[ parameters
R indices "F×3s#
R indices "all data#
8099
2838 "Rintꢁ9[9065#
2410 "F×3s#
2838
237
R0ꢁ9[9380\ wR1ꢁ9[0104
R0ꢁ9[9445\ wR1ꢁ9[0169
0[969
GOF]
2
Ä
Final Di}erence Peaks\ e:A
¦9[080\ −9[065
Ä
Table 1[ Selected Bond Distances in 0!C5H3"CO#1NCH1!1!C5H4CH1OCH1CH1!0\ 1!C1B09H09 "4#\ A
Bond
Bond
Bond
O12ÐC04
O16ÐC15
N03ÐC02
C0ÐB4
C0ÐB7
C1ÐB6
C04ÐC05
C06ÐC07
C19ÐC10
C18ÐC29
C20ÐC21
B2ÐB6
B2ÐB5
B3ÐB00
B4ÐB8
0[198"1#
0[310"1#
0[341"1#
0[696"2#
0[616"1#
0[600"2#
0[373"1#
0[272"2#
0[271"1#
0[253"2#
0[256"5#
0[661"2#
0[668"2#
0[668"2#
0[661"2#
0[655"3#
0[666"2#
0[665"2#
O13ÐC11
N03ÐC11
C0ÐC02
C0ÐB8
C1ÐC14
C1ÐB7
C05ÐC06
C07ÐC08
C10ÐC11
C18ÐC23
C21ÐC22
B2ÐB00
B3ÐB5
0[100"1#
0[284"1#
0[417"1#
0[698"2#
0[416"2#
0[611"2#
0[272"2#
0[267"3#
0[375"1#
0[258"2#
0[230"5#
0[662"2#
0[656"2#
0[671"2#
0[665"2#
0[661"2#
0[662"2#
0[673"3#
O16ÐC17
N03ÐC04
C0ÐC1
C0ÐB5
C1ÐB2
0[302"2#
0[288"1#
0[573"1#
0[611"1#
0[695"2#
0[621"1#
0[276"1#
0[278"2#
0[494"2#
0[267"4#
0[234"3#
0[663"2#
0[664"2#
0[655"2#
0[654"2#
0[669"2#
0[668"2#
0[676"2#
C1ÐB5
C05ÐC10
C08ÐC19
C14ÐC15
C29ÐC20
C22ÐC23
B2ÐB3
B3ÐB4
B3ÐB09
B4ÐB5
B6ÐB7
B8ÐB01
B09ÐB01
B4ÐB09
B6ÐB00
B7ÐB01
B8ÐB09
B00ÐB01
B6ÐB01
B7ÐB8
B09ÐB00

2283
Y[ Wu et al[
Table 2[ Selected Bond Angles in 0!C5H3"CO#1NCH1!1!C5H4CH1OCH1CH1!0\ 1!C1B09H09 "4#\ >
Bond
Angle
Bond
Angle
C17ÐO16ÐC15
C11ÐN03ÐC02
C02ÐC0ÐC1
C1ÐC0ÐB4
C1ÐC0ÐB8
C02ÐC0ÐB5
B4ÐC0ÐB5
C02ÐC0ÐB7
B4ÐC0ÐB7
B5ÐC0ÐB7
C14ÐC1ÐB2
C14ÐC1ÐB6
B2ÐC1ÐB6
000[3"1#
C11ÐN03ÐC04
C04ÐN03ÐC02
C02ÐC0ÐB4
C02ÐC0ÐB8
B4ÐC0ÐB8
C1ÐC0ÐB5
B8ÐC0ÐB5
C1ÐC0ÐB7
B8ÐC0ÐB7
C14ÐC1ÐC0
C0ÐC1ÐB2
C0ÐC1ÐB6
C14ÐC1ÐB7
B2ÐC1ÐB7
C14ÐC1ÐB5
B2ÐC1ÐB5
000[68"02#
012[43"02#
007[58"02#
012[05"03#
51[40"01#
50[03"09#
002[78"03#
59[53"00#
51[21"02#
019[64"03#
009[06"02#
009[99"03#
004[6"1#
012[77"03#
007[63"03#
009[47"02#
009[32"02#
002[61"02#
51[39"00#
010[00"03#
002[43"03#
002[06"02#
010[0"1#
007[4"1#
51[35"01#
59[81"09#
51[05"01#
59[40"09#
002[2"1#
003[39"02#
018[3"1#
010[3"1#
097[1"1#
010[5"1#
006[2"1#
029[5"1#
013[6"1#
094[78"03#
097[8"1#
007[5"1#
019[6"2#
C0ÐC1ÐB7
B6ÐC1ÐB7
C0ÐC1ÐB5
B6ÐC1ÐB5
002[6"1#
019[5"1#
51[20"00#
001[76"03#
013[6"1#
094[78"03#
029[3"1#
006[1"1#
010[1"1#
010[1"1#
097[1"1#
018[3"1#
006[1"1#
098[8"1#
019[6"2#
008[7"2#
019[3"2#
010[5"2#
094[3"1#
094[65"03#
59[19"02#
097[06"03#
48[54"01#
59[08"00#
097[1"1#
096[4"1#
096[6"1#
48[72"02#
47[68"00#
094[32"03#
097[5"1#
B7ÐC1ÐB5
N03ÐC02ÐC0
O12ÐC04ÐC05
C06ÐC05ÐC10
C10ÐC05ÐC04
C08ÐC07ÐC06
C10ÐC19ÐC08
C19ÐC10ÐC11
O13ÐC11ÐN03
N03ÐC11ÐC10
O16ÐC15ÐC14
C29ÐC18ÐC23
C23ÐC18ÐC17
C21ÐC20ÐC29
C21ÐC22ÐC23
C1ÐB2ÐB6
B6ÐB2ÐB00
B6ÐB2ÐB3
C1ÐB2ÐB5
B00ÐB2ÐB5
B5ÐB3ÐB2
B2ÐB3ÐB4
B2ÐB3ÐB00
B5ÐB3ÐB09
B4ÐB3ÐB09
C0ÐB4ÐB09
B09ÐB4ÐB8
B09ÐB4ÐB3
C0ÐB4ÐB5
B8ÐB4ÐB5
C0ÐB5ÐC1
C1ÐB5ÐB3
C1ÐB5ÐB4
C0ÐB5ÐB2
B3ÐB5ÐB2
C1ÐB6ÐB00
B00ÐB6ÐB01
B00ÐB6ÐB2
C1ÐB6ÐB7
B01ÐB6ÐB7
C1ÐB7ÐC0
C0ÐB7ÐB01
C0ÐB7ÐB6
C1ÐB7ÐB8
O12ÐC04ÐN03
N03ÐC04ÐC05
C06ÐC05ÐC04
C07ÐC06ÐC05
C07ÐC08ÐC19
C19ÐC10ÐC05
C05ÐC10ÐC11
O13ÐC11ÐC10
C15ÐC14ÐC1
O16ÐC17ÐC18
C29ÐC18ÐC17
C18ÐC29ÐC20
C22ÐC21ÐC20
C22ÐC23ÐC18
C1ÐB2ÐB00
C1ÐB2ÐB3
008[5"2#
019[9"2#
47[80"00#
48[61"02#
096[8"1#
48[46"00#
096[8"1#
59[21"00#
097[9"1#
48[78"02#
096[82"03#
48[42"01#
094[5"1#
59[27"01#
59[32"01#
48[19"00#
097[1"1#
47[23"09#
093[81"03#
094[19"03#
094[00"02#
59[92"01#
094[5"1#
59[70"03#
59[08"02#
48[12"00#
59[93"02#
47[33"09#
093[8"1#
094[14"03#
094[41"03#
48[87"02#
B00ÐB2ÐB3
B6ÐB2ÐB5
B3ÐB2ÐB5
B5ÐB3ÐB4
B5ÐB3ÐB00
B4ÐB3ÐB00
B2ÐB3ÐB09
B00ÐB3ÐB09
C0ÐB4ÐB8
C0ÐB4ÐB3
B8ÐB4ÐB3
B09ÐB4ÐB5
B3ÐB4ÐB5
C0ÐB5ÐB3
C0ÐB5ÐB4
B3ÐB5ÐB4
C1ÐB5ÐB2
B4ÐB5ÐB2
C1ÐB6ÐB01
C1ÐB6ÐB2
B01ÐB6ÐB2
B00ÐB6ÐB7
B2ÐB6ÐB7
C1ÐB7ÐB01
C1ÐB7ÐB6
B01ÐB7ÐB6
C0ÐB7ÐB8
097[1"1#
48[56"01#
094[07"03#
47[28"09#
59[03"01#
47[01"00#
096[7"1#
094[8"1#
47[52"01#
097[7"1#
097[6"1#
097[03"03#
094[1"1#
47[50"01#
48[70"02#
47[24"00#
096[5"1#
B01ÐB7ÐB8
B6ÐB7ÐB8
"continued on next pa`e#

Synthesis and characterization of a protected amino alcohol containing ortho!carborane
2284
Table 2 "continued#
Bond
Angle
Bond
Angle
C0ÐB8ÐB4
B4ÐB8ÐB01
B4ÐB8ÐB7
47[69"00#
097[9"1#
097[9"1#
094[9"1#
59[17"02#
097[0"1#
097[9"1#
48[88"02#
096[7"1#
48[69"02#
59[98"02#
097[9"1#
48[80"01#
48[52"03#
59[97"03#
59[04"02#
59[11"01#
097[9"1#
48[46"03#
096[7"1#
C0ÐB8ÐB01
C0ÐB8ÐB7
094[5"1#
48[23"00#
48[70"02#
48[53"01#
096[8"1#
48[87"01#
59[93"01#
097[9"1#
59[15"03#
097[0"1#
096[7"1#
097[9"1#
59[07"02#
096[7"1#
097[0"1#
097[0"1#
096[3"1#
59[92"02#
096[7"1#
48[55"02#
B01ÐB8ÐB7
B4ÐB8ÐB09
B7ÐB8ÐB09
B4ÐB09ÐB8
B4ÐB09ÐB3
B8ÐB09ÐB3
B00ÐB09ÐB01
B3ÐB09ÐB01
B6ÐB00ÐB09
B6ÐB00ÐB3
B09ÐB00ÐB3
B2ÐB00ÐB01
B3ÐB00ÐB01
B6ÐB01ÐB8
B6ÐB01ÐB09
B8ÐB01ÐB09
B7ÐB01ÐB00
B09ÐB01ÐB00
C0ÐB8ÐB09
B01ÐB8ÐB09
B4ÐB09ÐB00
B00ÐB09ÐB8
B00ÐB09ÐB3
B4ÐB09ÐB01
B8ÐB09ÐB01
B6ÐB00ÐB2
B2ÐB00ÐB09
B2ÐB00ÐB3
B6ÐB00ÐB01
B09ÐB00ÐB01
B6ÐB01ÐB7
B7ÐB01ÐB8
B7ÐB01ÐB09
B6ÐB01ÐB00
B8ÐB01ÐB00
Synthesis of HC2CCH1CH1OCH1C5H4 "0#
allowed to warm to room temperature and stirred
for one hour[ To this solution\ 1[9 g "9[955 mol# of
In a 149 cm2 round bottom ~ask were placed 6[9 g paraformaldehyde were added and stirring of the
"9[09 mol# of 2!butyn!0!ol and 099 cm2 of anhydrous resulting solution was continued for an additional
THF[ To the resulting suspension\ 1[7 g "9[00 mol# of 1 hrs[ The THF was removed by rotary evaporation
sodium hydride were added slowly[ After gas evol! and to the resulting residue\ 14 cm2 of distilled water
ution had ceased\ 08[9 g "9[00 mol# of benzyl bromide were added[ This solution was extracted with three
were added to the solution and stirred at room tem! 19 cm2 of anhydrous ether[ The ethereal solution was
perature overnight[ After 01 hrs\ a voluminous pre! dried over MgSO3[ The ether was then removed by
cipitate had formed[ The precipitate was _ltered and rotary evaporation[ The resulting oil was distilled and
the solvent removed by rotary evaporation[ The a colorless oil "7[1 g\ 9[932 mol\ 61) yield\ bp 029Ð
resulting residue was distilled under reduced pressure\ 021>C:9[4 mm Hg# was obtained and identi_ed as 4!
resulting in the isolation of a colorless oil which was benzylox!1!pentyn!0!ol[ 0H NMR] "CDCl2#\ 1[20 "0H\
identi_ed as benzyl!2!butynyl ether "01[2 g\ 9[966 mol\ t\ Jꢁ4[83 Hz#\ 1[41 "1H\ m#\ 2[46 "1H\ t\ Jꢁ5[77 Hz#\
66) yield\ bp 55Ð57>C:9[5 mm Hg#[ 0H NMR] 3[19 "1H\ m#\ 3[43 "1H\ s#\ 6[22 "4H\ m#[ 02C NMR]
"CDCl2#\ 0[87 "0H\ t\ Jꢁ1[53 Hz#\ 1[36 "1H\ d of t\ "CDCl2#\ 08[73 "CH1#\ 49[75 "HOCH1#\ 56[89
JABꢁ1[53 Hz\
JAXꢁ5[85 Hz#\
2[47
"1H\
t\ "CH1O#\ 61[58 "OCH1#\ 68[23 "C2#\ 71[50 "C2#\
Jꢁ5[85 Hz#\ 3[43 "1H\ s#\ 6[21 "4H\ m#\ 02C NMR] 016[16 "C5H4#\ 017[19 "C5H4#\ 026[55 "C5H4#[ IR
"CDCl2#\ 08[55 "CH1#\ 56[89 "CH1O#\ 58[10 "OCH1#\ "cm−0#] 2333 "s\ br#\ 1761 "s#\ 1139 "m#\ 0605 "m#\
61[60 "2C#\ 70[93 "HC2#\ 016[36 "C5H4#\ 017[08 0579 "sh#\ 0379 "w#\ 0345 "m#\ 0209 "m#\ 0161 "m#\
"C5H4#\ 026[71 "C5H4#\ IR "cm−0#] 2185 "s#\ 2917 "m#\ 0985 "m#\ 864 "m#\ 649 "m#\ 699 "m#[ MS "EI#] m:z
1757 "s#\ 1119 "w#\ 0619 "m#\ 0385 "m#\ 0345 "m#\ 0253 relative intensity 078 "M¦!H\ 2[5#\ 048 "M¦!HOCH1\
"m#\ 0164 "w#\ 0193 "w#\ 0099 "s#\ 0917 "m#\ 684 "w#\ 2[5#\ 010 "M¦!HOCH1C2CCH1\ 81[5#\ 002 "M¦!
639 "m#\ 699 "m#\ 537 "m#[ MS "EI#] m:z relative C5H4\ 6[0#\ 096 "M¦!HOCH1C2CCH1CH1\ 2[5#\ 72
intensity 048 "M¦!H\ 099#\ 096 "M¦!HC2CCH1CH1\ "M¦!OCH1C5H4\ 2[5#[
8[0#\ 72 "M¦!C5H4\ 11[6#[
Synthesis of BrCH1C2CCH1CH1OCH1C5H4 "2#
Synthesis of HOCH1C2CCH1CH1OCH1C5H4 "1#
In a 149 cm2 round bottom ~ask were placed 6[9 g
To a solution containing 8[5 g "9[959 mol# of benzyl! "9[926 mol# of HOCH1C2CCH1CH1OCH1C5H4 and
2!butynyl ether in 89 cm2 of dry THF kept at −19>C\ 09[9 g "9[935 mol# of "CH2#1NCHBr1\ which was pre!
20 cm2 "9[950 mol# of a 1[9 M solution n!BuLi in pared according to the literature procedure ð22Ł[ To
cyclohexane were added slowly[ The mixture was this mixture\ 099 cm2 of dry acetonitrile was added

2285
Y[ Wu et al[
and the resulting solution was heated to re~ux for Synthesis of 0!C5H3"CO#1NCH1!1!C5H4CH1OCH1
1 hrs[ The acetonitrile was removed in vacuo and the CH1!0\ 1!C1B09H09 "4#
resulting residue extracted with ether[ After evapora!
tion of the ether from the solution\ the extract was
In
a
099 cm2 round bottom ~ask\ 9[399 g
separated on a silica gel column chromatography "9[9922 mol# of decaborane "03# and 9[59 cm2
using a 1]0 mixture of hexanes:methylene chloride[ "9[997 mol# of dimethyl sul_de were dissolved in
The resulting oil obtained was identi_ed as benzyl!4! 24[9 cm2 of dry benzene[ The solution was stirred to
bromo!1!pentynyl ether[ "7[9 g\ 9[920 mol\ 74) yield#[ re~ux for 3 hrs[ After allowing the solution to cool to
0H NMR "CDCl2#\ 1[45 "1H\ m#\ 2[47 "1H\ t\ room temperature\ 0[92 g "9[9922 mol# of N!"4!ben!
Jꢁ5[77 HZ#\ 2[80 "1H\ t\ Jꢁ1[13 Hz#\ 3[44 "1H\ s#\ zyloxy!1!pentynyl#phthalimide were added quickly
6[23 "4H\ m#[ 02C NMR "CDCl2#\ 04[92 "BrCH1#\ and stirred at room temperature for 09 min[\ to ensure
19[02 "CH1#\ 56[50 "CH1O#\ 61[60 "OCH1#\ 66[26 complete dissolution of the alkyne[ The resulting solu!
"C2#\ 73[38 "C2#\ 016[32 "C5H4#\ 017[05 "C5H4#\ tion was then heated to re~ux for 09 hrs[ The benzene
026[57 "C5H4#[ IR "cm−0#] 2917 "m#\ 1757 "s#\ 1125 was removed in vacuo and to the resulting solid\
"m#\ 0619\ 0537 "w#\ 0385 "w#\ 0345 "s#\ 0253 "s#\ 0101 1[4 cm2 of methanol were added and stirred at room
"s#\ 0099 "s#\ 639 "s#\ 699 "s#\ 597 "s#[ MS "EI\ 70Br# temperature for 3 hrs[ The suspension was _ltered\
m:z relative intensity 144 "M¦¦H\ 4[2#\ 143 "M¦\ resulting in a white solid which was washed with three
3[0#\ 141 "M!1¦\ 0[1#\ 062 "M¦!Br\ 24[7#\ 048 "M¦! portions of 4[9 cm2 of cold ethanol[ The white solid
BrCH1\ 1[5#\ 036 "M¦!BrCH1C\ 2[9#\ 032 "M!1¦! was dissolved in a 0]0 mixture of CH2CN:CH1Cl1
HOCH1C5H4\ 099#\ 010 "M¦!BrCH1C2CCH1\ 3[6#\ and recrystallized from this solution\ resulting in the
097 "M¦!BrCH1C2CCH1CH1\ 1[0#\ 66 "M¦! isolation of 0!methylphthalimido!1!ethylbenzyl ether!
BrCH1C2CCH1CH1O\ 04[8#[
o!carborane "9[69 g\ 49) yield\ mp 0064Ð066>C#[ The
identity of this compound was con_rmed by a single
crystal X!ray di}raction study[ 0H NMR]
Synthesis of C5H3"CO#1NCH1C2CCH1CH1OCH1 "CD2C"O#CD2#\ 2[93 "1H\ t\ Jꢁ4[75 Hz#\ 2[66 "1H\ t\
C5H4 "3#[
Jꢁ4[75 Hz#\ 3[45 "1H\ s#\ 3[46 "1H\ s#\ 6[24 "4H\ m#\
6[78 "3H\ m#[ 02C NMR "CD2C"O#CD2#\ 24[57 "CH1#\
A solution consisting of 1[42 g "9[909 mol# of 39[38 "CH1#\ 57[68 "CH1O#\ 62[15 "OCH1#\ 67[05 "car!
BrCH1C2CCH1CH1OCH1C5H4 dissolved in 04 cm2 borane C#\ 79[78 "carborane C#\ 013[19 "C5H4#\ 017[05
of DMF was added to 1[93 g "9[900 mol# of potassium "C5H4#\ 017[65 "C5H4#\ 020[84 "C5H4#\ 024[29 "C5H4#\
phthalimide and stirred at room temperature over! 027[25 "C5H4#\ 056[25 "C1O#[ 00B NMR]
night[ After that time\ 49 cm2 of distilled water was "CD2C"O#CD2#\ −9[37 "1B#\ −4[38 "7B#[ The coup!
added to the solution and the mixture extracted with ling constants for this compound could not be reliably
three 19 cm2 portions of chloroform[ This solution determined due to coincidental overlap of signals[ IR
was dried over MgSO3 and the chloroform stripped "cm−0#] 1885 "m#\ 1777 "m#\ 1479 "s#\ 0665 "s#\ 0613
o} in vacuo[ The residue was dissolved in a minimal "s#\ 0501 "w#\ 0373 "m#\ 0357 "w#\ 0345 "w#\ 0319 "m#\
amount of methylene chloride and separated via silica 0399 "s#\ 0253 "s#\ 0177 "m#\ 0025 "m#\ 0093 "s#\ 0979
gel column chromatography[ This resulted in the "s#\ 0925 "m#\ 859 "m#\ 753 "w#\ 737 "w#\ 713 "w#\ 681
isolation of a viscous oil which was identi_ed "w#\ 641 "m#\ 605 "s#\ 699 "m#\ 535 "w#\ 597 "w#\ 417
as N!"4!benzyloxy!1!pentynyl#phthalimide "2[94 g\ "m#[ MS "EI#\ m:z relative intensity 328 "M¦\ 5[4#\
0
9[9985 mol\ 85) yield#[ H NMR] "CD2C"O#CD2#\ 237 "M¦!CH1C5H4\ 6[5#\ 221 "M¦!OCH1C5H4\ 31[6#\
1[34 "1H\ m#\ 2[42 "1H\ t\ Jꢁ6[01 Hz#\ 3[30 "1H\ t\ 292 "M¦!H and CH1CH1OCH1C5H4\ 6[7#\ 059
Jꢁ1[13 Hz#\ 3[49 "1H\ s#\ 6[29 "4H\ m#\ 6[75 "3H\ m#[ "M¦!C1B09H09CH1CH1OC5H4\ 03[3#\ 096 "M¦!
02C NMR] "CD2C"O#CD2#\ 19[97 "CH1#\ 16[25 "CH1#\ C5H3"CO#1NCH1C1B09H09CH1CH1\ 28[6#\ 80 "M¦!
57[49 "CH1O#\ 61[56 "OCH1#\ 64[33 "C2#\ 79[43 C5H3"CO#1NCH1C1B09H09CH1CH1O\ 099#\ 66 "M¦!
"C2#\ 012[54 "C5H4#\ 016[75 "C5H4#\ 017[56 "C5H4#\ C5H3"CO#1NCH1C1B09H09CH1CH1OCH1\ 04[8#[
021[46 "C5H4#\ 023[75 "C5H4#\ 028[12 "C5H4#\ 056[11
"C1O#[ IR "cm−0#] 2919 "m#\ 1761 "m#\ 1134 "w#\
0661 "s#\ 0605 "s#\ 0549 "m#\ 0449 "w#\ 0419 "w#\ 0319 Synthesis of 0!C5H3"CO#1NCH1!1!HOCH1CH1!0\ 1!
"m#\ 0281 "m#\ 0219 "m#\ 0005 "s#\ 833 "m#\ 613 "s#\ C1B09H09 "5#
517 "m#\ 421 "m#[ MS "EI#\ m:z relative intensity 219
"M¦¦H\ 4[8#\ 101 "M¦!OCH1C5H4\ 2[9#\ 087 "M¦!
In
a
4[9 cm2 round bottom ~ask\ 9[934 g
CH1OCH1C5H4\ 4[2#\ 062 "M¦!C5H3"CO#1N\ 7[2#\ "9[09 mmol# of 0!methylphthalimido!1!ethylbenzyl
061 "M¦!CH1CH1OCH1C5H4\ 10[5#\ 059 "M¦! ether!o!carborane were placed and 9[49 cm2 of CHCl2
C2CCH1CH1OCH1C5H4\
31[3#\
048
"M¦! added[ To the resulting solution\ 9[49 cm2 of ethanol
C5H3"CO#1NCH1\ 72[1#\ 020 "M¦!CO and and 29 mg of Pd:C were added[ The ~ask was then
HC2CCH1CH1OCH1C5H4\ 2[4#\ 093 "M¦!CO and attached to a three!way vacuum stopcock\ the con!
NCH1C2CCH1CH1OCH1C5H4\ 04[0#\ "M¦!80"M¦! tents frozen and degassed[ A balloon _lled with H1
C5H3"CO#1NCH1C2CCH1CH1\ 099#\ 66 "M¦! gas was then attached to the three!way vacuum stop!
C5H3"CO#1NCH1C2CCH1CH1OCH1\ 01[7#[
cock and opened to _ll the ~ask with an atmosphere

Synthesis and characterization of a protected amino alcohol containing ortho!carborane
2286
of hydrogen[ The solution was then stirred at room OCH1C5H4 group\ exhibits a coupling constant of
temperature overnight[ The solution was then _ltered 5[85 Hz\ matching that of the triplets of the resonance
to remove the catalyst and the solvent was removed at d 1[36 ppm[ The benzylic hydrogens appear as a
in vacuo[ The resulting residue was dissolved in CH1Cl1 singlet at 3[43 ppm\ typical of benzylic protons[ The
and puri_ed via column chromatography "packed IR spectra also shows the typical peaks\ especially the
with silica gel#[ The elutant used was a 1) CH2OH C2C triple bond stretch\ which is found at 1119 cm−0
\
mixture in CH1Cl1[ This resulted in the isolation also typical for this class of compounds[ The 02C NMR
of 18 mg of a white solid\ which was identi_ed consists of eight resonances\ at the typical shifts for
as 0!methylphthalimido!1!ethylalcohol!o!carborane the type of functional groups present in compound 0[
0
"9[918 g\ 9[972 mmol\ 72) yield\ mp 026Ð028>C#[ H
The next step in the synthesis of the alkyne pre!
NMR] "CD2CN#\ 1[72 "1H\ t\ Jꢁ5[49 Hz#\ 2[09 "0H\ cursor is the preparation of the amino end of the
t\ Jꢁ4[19 Hz#\ 2[64 "1H\ m\ JABꢁ5[49 Hz\ molecule[ Care had to be taken in choosing an appro!
JAXꢁ4[19 Hz#\ 3[36 "1H\ s#\ 6[75 "3H\ m#[ 02C NMR] priate procedure that would carry the protected
"CD2CN#\ 27[13 "CH1#\ 30[07 "CH1#\ 50[04 "CH1O#\ alcoholic part of the alkyne intact[ For this reason\
67[78 "carborane C#\ 70[42 "carborane C#\ 013[54 the reaction of 0 with n!BuLi\ followed by the addition
"C5H4#\ 021[41 "C5H4#\ 024[89 "C5H4#\ 057[44 "C1O#[ of paraformaldehyde was chosen[ The method is sim!
00B NMR] "CD2CN#\ 9[78 "0B\ JBHꢁ018 Hz#\ −9[78 ple and does not result in deprotection of the benzylic
"0B\ JBHꢁ018 Hz#\ −3[65 "3B\ the coupling constant group to form the corresponding alcohol[ Compound
for this peak could not be reliably be calculated due 1 was isolated in reasonable yield "61)#\ as a colorless
to coincidental overlap of signals#\ −4[33 "3B\ air stable oil[ The identi_cation of this compound was
JBHꢁ017 Hz#[ IR "cm−0#] 2425 "s#\ 2333 "br#\ 1845 not as straightforward as that of 0[ The presence of
"w# 1485 "s#\ 0665 "m#\ 0605 "s#\ 0377 "m#\ 0319 "m#\ multiplets at d 1[41 ppm and d 3[19 ppm\ each due to
0399 "s#\ 0259 "m#\ 0039 "w#\ 0977 "w#\ 0943 "w#\ 859 two set of protons\ prevents an analysis based on
"w#\ 605 "m#\ 421 "w#[ MS "EI#\ m:z relative intensity\ coupling constants as that performed for 0[ Nonethe!
238 "M¦\ 76[7#\ 237 "M¦!H\ 30[0#\ 220 "M¦!H1O\ less\ the peak as d 1[20 ppm\ is due to the OH group
76[5#\ 029 "M¦!HOCH1CH1C1B09H09\ H1 and CO\ and the resonance at d 2[46 ppm is due to the CH1O
099#[
group[ The other two resonances\ d 1[41 and d
3[19 ppm respectively are assigned to the CH1 groups
bonded to the C2C bond[ The down_eld resonance
is that of the CH1 group bonded to the OH and the
other one corresponds to the other CH1 group[ The
RESULTS AND DISCUSSION
In order to prepare the desired precursor\ it was fact that the obtained coupling constants are similar
necessary to _rst synthesize the corresponding alkyne in value\ resulted in the observed multiplets for these
needed for the reaction with decaborane "03#[ This resonances[ The benzylic protons were assigned to the
procedure was a multistep synthesis starting from 2! resonance at d 3[43 ppm\ again typical for these type
butyn!0!ol\ which is the commercially available alkyne of protons[ The 02C NMR showed nine resonances\
needed for the synthesis of the desired alkyne[ The which is the expected number of resonances for com!
synthesis of 0 was accomplished by adapting the pound 1[ The IR spectra was more informative\ the
reported literature procedure ð22Ł[ The isolation of presence of a broad peak at 2339 cm−0\ typical of a
benzyl!2!butynyl ether in signi_cant yield "66)# OH group\ coupled with a resonance at 1139 cm−0
allowed for the continuation of the proposed synthetic assignable to the C2C triple bond\ indicated the for!
scheme\ shown in Fig[ 0[ The identity of this com! mation of 1[ Based on this information\ the fact that
0
pound was determined by H and 02C NMR\ mass the benzylic group was left intact\ as indicated by the
spectrometry\ as well as IR spectroscopy[ The nature 0H and 02C NMR data\ the task of continuing toward
of 0\ an air stable colorless oil\ allowed for the easy the formation of the alkyne precursor could be con!
handling of this compound[ The 0H NMR data shows tinued[
an interesting pattern of resonances[ The proton
Compound 2 was prepared by the reaction of 1
assigned to the terminal hydrogen of the alkyne with "CH2#1NCHBr1[ This procedure resulted in the
appears at d 0[87 ppm\ as a triplet[ Obviously there is bromination of the CH1 group carrying the alcohol\
coupling between this proton and the CH1 group next while keeping the protected alcohol on the other side
to the b!carbon of the alkyne\ even though they are of the alkyne una}ected[ The isolated yield "74)#
separated by four bonds[ This is con_rmed by the of the colorless oil\ which was puri_ed by column
splitting of resonances arising from the CH1 group of chromatography was high enough to allow the con!
0
protons bonded directly to the alkylinic carbon\ these tinuation of the synthetic strategy proposed[ The H
protons show a resonance at d 1[36 ppm\ as a doublet and 02C NMR data agrees with the formulation of
of triplets[ The coupling constant of the doublets is compound 2[ The IR spectra also showed the presence
1[53 Hz\ which corresponds to the coupling constant of the C2C triple bond\ which is of paramount
obtained for the triplet at d 0[87 ppm[ Furthermore\ importance for the synthesis of the sought carborane[
the down_eld triplet at d 2[47 ppm\ assigned to the The mildness of the bromination method and the ease
CH1 group bonded to that CH1 group and to the of synthesis of 2 in high yield is an attractive feature of

2287
Y[ Wu et al[
Fig[ 0[ Reaction sequence leading to the synthesis of heterodisubstituted ortho!carboranes[
this synthetic strategy[ Compound 2 is the immediate is ample evidence of the identity of every intermediate
precursor to the protected amino alcohol alkyne leading to its formation[
sought for the preparation of carborane 4[
0
The identity of 4 is supported by the H\ 00B\ and
The preparation of compound 3 was accomplished 02C NMR data\ as well as the IR spectra\ mass spec!
by using Gabriel|s reagent\ potassium phthalimide\ trometry and the single crystal X!ray di}raction study
this allowed for the convenient preparation of the of this compound[ An ORTEP diagram for this com!
protected amine in high yield "85)#[ Compound 3 pound is shown in Fig[ 1[
was isolated as a viscous oil[ The 0H NMR showed a
The 0H NMR data shows the expected peaks for a
multiplet at d 1[34 ppm\ assignable to CH1 protons compound of this type[ The triplet at d 2[93 ppm is
bonded to the b!carbon of the alkyne\ a triplet at d due to the CH1 group of the ethylene unit in the
2[42 ppm\ corresponding to the NCH1 group\ a triplet carborane\ which is coupled to the CH1 group of the
at d 3[30 ppm\ due to the CH1O group\ a singlet at d ether moiety and the CH1 group of the phthalimide
3[49 ppm\ for the benzylic protons of the protected unit[ The triplet at d 2[66 ppm is due to the other CH1
alcohol\ an two di}erent sets of aromatic multiplets of the ethylene group in this carborane[ The coupling
at d 6[29 and d 6[73 ppm\ respectively\ due to the constants were found to be identical for these protons\
OCH1C5H4 and C5H3"CO#1N groups[ The 02C NMR indicating that they are neighbors[ The singlets at d
of 3 should consist of thirteen peaks\ which were 3[45 and d 3[46 ppm respectively are the result of the
observed[ The C1O resonance was found at d protons in the CH1 group linked to the oxygen atom
056[11 ppm\ typical for an amide group[ The IR spec! of the ether unit and the CH1 group in the phthalimide
tra of 3 also indicated its identity[ The weak resonance unit[ The expected multiplets\ consisting of 3 protons
at 1134 cm−0 coupled with the strong carbonyl stretch and 4 protons respectively\ are due to the benzene
at 0605 cm−0 clearly indicated that compound 3 was groups present in this molecule[ The 02C NMR data
formed[ The high yield of this reaction indicates that shows the expected thirteen peaks[ The presence of
this is a convenient method to prepare the desired the carbonyl resonance at d 056[25 ppm clearly indi!
precursor[ The next step is simply the reaction of cates that the alkyne incorporated into the cage[ This
decaborane "03# in the presence of dimethyl sul_de fact coupled to the resonances are d 67[05 and d
with 3\ in order to produce the sought compound[
79[78 ppm\ assignable to the carborane carbons
The identities of compounds 0 through 3 were fur! showed that the expected product was indeed syn!
ther con_rmed by mass spectrometric experiments and thesized[
the synthesis and characterization of compound 4[
The IR data for 4 further supports the identity of
The single crystal X!ray structure determination of 4 this compound[ Peaks at 1447 cm−0\ typical of BÐH

Synthesis and characterization of a protected amino alcohol containing ortho!carborane
2288
Fig[ 1[ ORTEP drawing of 0!C5H3"CO#1NCH1!1!C5H4CH1OCH1CH1!0\ 1!C1B09H09 "4# with 29) probability thermal
ellipsoids[
stretches\ coupled with peaks at 0665 and 0613 cm−0 for the carbon!carbon bond length range from a mini!
Ä
respectively\ due to the carbonyl groups of the phthali! mum of 0[581 "7# A for 1!bromo!0!phenyl!0\ 1!
mide unit are indicative of the incorporation of the dicarba!closo!dodecaborane "01# ð28Ł\ which could be
alkyne into the decaborane "03# framework[
argued to be the less sterically demanding of these
The single X!ray data shows the expected bond compounds and therefore closer in electronic structure
Ä
distances for a compound of this type[ The boron! to that of 4 to a maximum of 0[658 "3# A in 0!diiso!
boron distances are within the expected range\ 0[654 propylphosphino!1!phenyl!0\ 1!dicarba!closo!dode!
Ä
to 0[676 A\ typical of these type of compounds[ The caborane "01# ð39Ł\ which would be more sterically
carbon!carbon in the cage and the boron!carbon dis! demanding and dissimilar to the electronic structure
Ä
tances are also typical\ 0[573 to 0[621 A[ This clearly of 4[ The argument used for the lengthening of the
indicates that the steric e}ects imposed by the sub! carbon!carbon bond in these compounds is the partial
stituent groups are minimal\ since in systems like overlap of tangentially oriented p orbitals of the clus!
0!diphenylphosphino!1!methyl!0\
1!dicarba!closo! ter carbon with orbitals having the appropriate sym!
dodecaborane "01# ð23Ł\ 0!diphenylphosphino!1! metry in the exopolyhedral group[ When the overlap
phenyl!0\ 1!dicarba!closo!dodecaborane "01# ð24Ł\ 0! is between a sp2 hybridized carbon and the cluster
phenyl!1!"tert!butyldimethylsilyl#!0\ 1!dicarba!closo! carbon\ no signi_cant e}ect should be observed\ as is
dodecaborane "01# ð25Ł\ 0!phenyl!1!trimethylsilyl!0\ the case in compound 4[
1!dicarba!closo!dodecaborane "01# ð26Ł\ 0!diiso!
The relative importance of the characterization of
propylphosphino!1!methyl!0\ 1!dicarba!closo!dode! 4 lies in the fact that a viable precursor to an amino
caborane "01# ð27Ł\ 0\ 1!Bis"diisopropylphosphino#!0\ acid containing carborane has been isolated[ The
1!dicarba!closo!dodecaborane "01# ð27Ł\ 1!bromo!0! exploration of its chemistry could potentially lead to
phenyl!0\ 1!dicarba!closo!dodecaborane "01# ð28Ł\ 0! the synthesis of such a compound\ which could prove
diisopropylphosphino!1!phenyl!0\ 1!dicarba!closo! useful in BNCT[
dodecaborane "01# ð39Ł\ and 0!phenyl!1!methyl!0\ 1!
The identity of compound 5 is based on the 0H\ 00B\
dicarba!closo!dodecaborane "01# ð30Ł the carbon!car! 02C NMR\ IR spectral and mass spectrometric data
0
bon bond length is signi_cantly lengthened due to the obtained[ The H NMR consists of two triplets at d
steric constraints placed by the exopolyhedral groups 1[72 and d 2[09 ppm of relative intensities two and one
in the cage[ The values obtained in these compounds respectively[ The _rst triplet is due to the CH1 group

2399
Y[ Wu et al[
1[ Vardarajan\ A[ and Hawthorne\ M[ F[\ Biocon!
ju`ate Chem[\ 0880\ 1\ 131Ð142[
2[ Kahl\ S[ B[ and Kasar\ R[ A[\ J[ Am[ Chem[ Soc[\
0885\ 007\ 0112Ð0113[
3[ Heying\ T[ L[\ Ager\ J[ W[ Jr[\ Clark\ S[ L[\ Mang!
old\ D[ L[\ Goldstein\ H[ L[\ Hillman\ M[\ Pollack\
R[ J[ and Szymanski\ J[ W[\ Inor`[ Chem[\ 0852\
1\ 0978Ð0981[
4[ Fein\ M[ M[\ Bobinski\ J[\ Mayes\ N[\ Schwartz\
N[ and Cohen\ M[ S[\ Inor`[ Chem[\ 0852\ 1\ 0000Ð
0004[
5[ Fein\ M[ M[\ Grafstein\ D[\ Paustian\ J[ E[\ Bobin!
ski\ J[\ Liechstein\ B[ M[\ Mayes\ M[\ Schwartz\
N[ N[ and Cohen\ M[ S[\ Inor`[ Chem[\ 0852\ 1\
0004Ð0008[
6[ Dupont\ J[ A[ and Hawthorne\ M[ F[\ J[ Am[
Chem[ Soc[\ 0853\ 75\ 0532[
7[ Zakharkin\ L[ I[\ Stanko\ V[ I[\ Brattsev\ V[ A[\
Chapovskii\ Yu[ A[\ Klimova\ A[ I[\ Oxlobystin\
O[ Yu[ and Ponomarenko\ A[ A[\ Dokl Akad[
Nauk SSSR\ 0853\ 044\ 0008Ð0011[
8[ Kutal\ C[ R[\ Owen\ D[ A[ and Todd\ L[\ J[ Inor`[
Synth[\ 0857\ 00\ 08Ð12[
09[ Paxson\ T[ E[\ Callahan\ K[ P[ and Hawthorne\
M[ F[\ Inor`[ Chem[\ 0862\ 01\ 697Ð698[
00[ Fukuda\ H[\ Hiratsuka\ J[ and Honda\ C[\ Radiat[
Res[\ 0883\ 027\ 324Ð331[
01[ Mallesch\ J[ L[\ Moore\ D[ E[\ Allen\ B[ J[\
McCarthy\ W[ H[\ Jones\ R[ and Stenning\ W[ A[\
Int[ J[ Radiat[ Oncol[ Biol[ Phys[\ 0883\ 17\ 0072Ð
0077[
02[ Wilson\ G[ J[\ Anisuzzaman\ A[ K[ M[\ Alam\ F[
and Soloway\ A[ H[\ Inor`[ Chem[\ 0881\ 20\ 0844[
03[ Heying\ T[ L[\ Ager\ J[ W[ Jr[\ Clark\ S[ L[\ Alex!
ander\ R[ P[\ Papetti\ S[\ Reid\ J[ A[ and Trotz\ S[
I[\ Inor`[ Chem[\ 0852\ 1\ 0986Ð0094[
04[ Hawthorne\ M[ F[\ An`ew[ Chem[ Int[ Ed[ En`l[\
0882\ 21\ 849[
05[ Fairchild\ R[ G[ and Bond\ V[ P[\ Int[ J[ Radiat[
Oncol[ Biol[ Phys[\ 0874\ 00\ 720[
06[ Shelly\ K[\ Hawthorne\ M[ F[ and Knobler\ C[ B[\
in Advances in Neutron Capture Therapy\ eds[ A[
H[ Soloway et al[ Plenum Press\ New York\ NY\
0882\ pp[ 214[
07[ Wyzlic\ I[ M[ and Soloway\ A[ H[\ Tetrahedron
Lett[\ 0881\ 22\ 6378[
08[ Sjoberg\ S[\ Hawthorne\ M[ F[\ Lindstrom\ P[\
Malmquist\ J[\ Carlsson\ J[\ Andersson\ A[ and
Petterson\ O[\ in Advances in Neutron Capture
Therapy\ eds[ A[ H[ Soloway et al[ Plenum Press\
New York\ NY\ 0882\ pp[ 158[
bonded directly to the cluster carbon[ Its coupling
constant of 5[49 Hz\ which corresponds to one of the
coupling constants found in the resonance at d
2[64 ppm\ allows for the identi_cation of these
protons\ as well as those at d 2[64 ppm\ which is a
triplet of doublets[ The coupling constant of the doub!
lets is 4[19 Hz\ which corresponds to the coupling con!
stant found for the resonance at d 2[09 ppm\ assigned
to the alcoholic proton[ The singlet at d 3[36 ppm is
due to the CH1 group in the phthalimide unit[ The
down_eld multiplet of area four is due to the phenyl
group in the compound[ The 02C NMR shows a total
of nine peaks\ which the number of resonances
expected for compound 5[
The IR spectral data shows the expected OH stretch
at 2333 cm−0\ as well as the expected BH and C1O
stretches in the normal regions[
The 00B NMR data\ as mentioned earlier consists
of four peaks\ of relative intensities 0]0]3]3[ The signals
observed are not the expected pattern of signals for a
compound of this type\ but similarly hetero!
disubstituted compounds had shown the same type of
pattern in the 00B NMR spectra ð31\ 32Ł[ The coinci!
dental overlap of resonances in the 00B NMR time
scale is not unprecedented\ a relevant example for the
observation of this type of pattern in the 00B NMR
spectrum is 0!phenyl!1!methyl!0\ 1!dicarba!closo!
dodecaborane "01# ð30Ł\ which is also a bifunctionally
substituted ortho!carborane[
With the isolation of compound 5\ the goal of pre!
paring an amino acid ortho!carborane derivative is
in principle possible[ Unfortunately\ all attempts to
isolate this compound have proven unsuccessful at
this time[ Although there is some evidence that upon
deprotection of the phthalimide group and oxidation
of the alcohol\ a compound that could possibly be the
amino acid carborane is formed\ its isolation has not
been possible[ The conditions upon which the depro!
tection is being carried out might be too harsh and
unwanted side reactions could be taking place[ We
are continuing to investigate alternate routes for the
preparation of the amino acid carborane and the
results from this e}ort will be reported in the future[
Supportin` information available*Tables of bond lengths
and angles\ atomic coordinates and thermal parameters "09
pages# are available[ Order information is available on any
current masthead page[
19[ Barth\ R[\ Soloway\ A[ H[\ Adams\ D[ M[ and
Alam\ F[ in Pro`ress in Neutron Capture Therapy
for Cancer\ eds[ B[ J[ Allen et al[ Plenum Press\
New York\ NY\ 0881\ pp[ 132[
10[ Anisuzzaman\ A[ K[ M[\ Alam\ F[ and Soloway\
A[ H[\ Polyhedron\ 0889\ 8\ 780[
11[ Tjarks\ W[\ Anisuzzaman\ A[ K[ M[ and Soloway\
A[ H[\ Nucleosides and Nucleotides\ 0881\ 00\
0654[
Acknowled`ements*The authors wish to thank the National
Science Foundation "Grant è CHE!8491395# for support of
this research[ We also thank Mr[ Monte Mauldin for his help
in the collection of 0H and 00B and 02C NMR data[
12[ Yamamoto\ Y[\ Pure Appl[ Chem[\ 0880\ 52\ 312[
13[ Schinazi\ R[ F[\ Goudgoan\ N[ M[\ Lesnikowski\
Z[\ Fulcand\ G[\ El Kattan\ Y[\ Ullas\ G[\ Mora!
vek\ J[ and Liotta\ D[ C[\ Int[ J[ Radiat[ Oncol[
Biol[ Phys[\ 0883\ 17\ 0002[
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14[ Shelly\ K[\ Feakes\ D[ A[\ Hawthorne\ M[ F[\

Synthesis and characterization of a protected amino alcohol containing ortho!carborane
2390
Schmidt\ P[ G[\ Krisch\ T[ A[ and Bauer\ W[ F[\ 23[ Kivekas\ R[\ Sillanpaa\ R[\ Teixidor\ F[ and
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à Ã
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Molecular Structure Corporation\ 0874 + 0881[
20[ SIR81] Altomare\ A[\ Burla\ M[ C[\ Camalli\ M[\
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à Ã
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and Nunez\ R[\ Abad\ M[\ Acta Cryst[\ 0884\ C40\
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0753Ð0757[
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0884\ C40\ 538Ð540[
39[ Sillanpaa\ R[\ Kivekas\ R[\ Teixidor\ F[\ Vinas\ C[
à Ã
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Ã
½
and Nunez\ R[\ Acta Cryst[\ 0885\ C41\ 1112Ð
1114[
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0884\ C40\ 535Ð538[
31[ Todd\ L[ J[ and Siedle\ A[ R[\ Pro`[ in NMR
Spectrosc[\ 0868\ 02\ 76Ð065[
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formations] A Guide to Functional Group Prep!
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Moeller\ K[ D[ J[ Or`[ Chem[\ 0876\ 41\ 3536Ð
3559[ c# Hart\ D[ J[\ Hong\ W[!P[ and Hsu\ L[!Y[
J[ Or`[ Chem[\ 0876\ 41\ 3554Ð3562[

2391
Y[ Wu et al[
Table 3[ Re_ned Positional Parameters for 0!C5H3"CO#1NCH1!1! C5H4CH1OCH1CH1!0\ 1!C1B09H09
"4#0
1
Ä
Atom
x
y
z
Ueq\ A
O12
O13
O16
N03
C0
9[25047"02#
9[31107"03#
9[54608"01#
9[28324"02#
9[2353"1#
9[2499"1#
9[3370"1#
9[2488"1#
9[2146"1#
9[1721"1#
9[1505"1#
9[1798"1#
9[2126"1#
9[2342"1#
9[2801"1#
9[3308"1#
9[4666"1#
9[6735"1#
9[7605"1#
9[8348"1#
0[9149"2#
0[9162"2#
9[8436"3#
9[7674"2#
9[2020"1#
9[1714"1#
9[2948"1#
9[3099"1#
9[0854"1#
9[1110"1#
9[0896"1#
9[0353"1#
9[0493"1#
9[9827"1#
−9[96572"00#
9[12619"00#
9[27738"00#
9[09904"01#
9[12533"03#
9[2762"1#
9[0617"1#
−9[91044"03#
−9[9528"1#
−9[0647"1#
−9[0780"1#
−9[9838"1#
9[9064"1#
9[9200"1#
9[0264"1#
9[3483"1#
9[3756"1#
9[3955"2#
9[2049"1#
9[2283"1#
9[1429"4#
9[0321"4#
9[0086"2#
9[1933"1#
9[3263"1#
9[2960"1#
9[0790"1#
9[2985"1#
9[3266"1#
9[2019"1#
9[0700"1#
9[1160"1#
9[2751"1#
9[2972"1#
9[95997"02#
9[36812"02#
9[2981"1#
9[14074"03#
9[0097"1#
9[0588"1#
9[0774"1#
9[0713"1#
9[1785"1#
9[1667"1#
9[2877"2#
9[4159"2#
9[4268"1#
9[3061"1#
9[2837"1#
9[2975"1#
9[2904"1#
9[1847"3#
9[2214"1#
9[3547"2#
9[3870"3#
9[2851"6#
9[1538"4#
9[1221"2#
9[9298"1#
−9[0123"1#
−9[9586"1#
9[9103"1#
9[0296"2#
9[0750"2#
9[9219"1#
−9[0065"2#
−9[9446"2#
9[9300"2#
9[9417"2#
9[9472"3#
9[9444"3#
9[9283"2#
9[9395"3#
9[9338"3#
9[9310"3#
9[9396"3#
9[9324"3#
9[9593"4#
9[9618"6#
9[9577"5#
9[9445"4#
9[9315"3#
9[9313"3#
9[9434"4#
9[9470"4#
9[0036"02#
9[9473"4#
9[9662"6#
9[010"1#
C1
C02
C04
C05
C06
C07
C08
C19
C10
C11
C14
C15
C17
C18
C29
C20
C21
C22
C23
B2
B3
B4
B5
B6
B7
B8
B09
B00
B01
9[024"1#
9[0095"01#
9[9678"6#
9[9382"4#
9[9376"4#
9[9336"4#
9[9311"3#
9[9446"5#
9[9498"4#
9[9402"4#
9[9446"4#
9[9454"5#
9[9487"5#
Ueqꢁ0:2ðU00"aaꢀ#1¦U11"bbꢀ#1¦U22"ccꢀ#1¦1U01aaꢀbbꢀcosg¦1U02aaꢀccꢀcosb¦1U12bbꢀccꢀcos aŁ

Synthesis and characterization of a protected amino alcohol containing ortho!carborane
2392
Table 4[ Re_ned Positional Parameters of Hydrogen Atoms for 0!C5H3"CO#1NCH1!1!C5H4CH1OCH1CH1!
0\ 1!C1B09H09 "4#1
1
Ä
Atom
x
y
z
Ueq\ A
H02a
H02b
H06
H07
H08
H19
H14a
H14b
H15a
H15b
H17a
H17b
H29
H20
H21
H22
H23
H2
H3
H4
H5
H6
H7
H8
H09
H00
H01
9[3861"1#
9[4973"1#
9[1585"1#
9[1222"1#
9[1549"1#
9[2260"1#
9[3919"1#
9[3376"1#
9[4659"1#
9[5020"1#
9[7066"1#
9[6717"1#
9[8322"1#
0[9653"2#
0[9685"2#
9[8460"3#
9[7181"2#
9[252"1#
9[295"1#
9[240"1#
9[403"1#
9[062"1#
9[110"1#
9[051"1#
9[965"1#
9[976"1#
9[0108"1#
9[1215"1#
−9[1284"1#
−9[1522"1#
−9[0957"1#
9[9700"1#
9[4238"1#
9[3051"1#
9[3886"1#
9[4478"1#
9[3750"2#
9[3996"2#
9[3030"1#
9[1583"4#
9[9732"4#
9[9349"2#
9[0763"1#
9[411"1#
9[295"1#
9[985"1#
9[296"1#
9[410"1#
9[203"1#
9[986"1#
9[062"1#
9[328"1#
9[0113"1#
9[1512"1#
9[0810"1#
9[2833"2#
9[5941"2#
9[5126"1#
9[2380"1#
9[2624"1#
9[1026"1#
9[2684"1#
9[2473"3#
9[0884"3#
9[4237"2#
9[4775"3#
9[3079"6#
9[0848"4#
9[0305"2#
9[932"1#
9[945
9[945
9[979
9[986
9[980
9[963
9[962
9[962
9[966
9[966
9[042
9[042
9[092
9[059
9[068
9[036
9[094
9[946"4#
9[944"4#
9[936"4#
9[930"3#
9[955"5#
9[950"5#
9[951"5#
9[955"5#
9[955"5#
9[958"5#
−9[110"1#
−9[008"1#
9[921"1#
9[109"1#
9[180"1#
9[933"1#
−9[104"1#
−9[096"1#
9[943"1#
−9[997"1#
9[209"1#
Ueqꢁ0:2ðU00"aaꢀ#1¦U11"bbꢀ#1¦U22"ccꢀ#1¦1U01aaꢀbbꢀcosg¦1U02aaꢀccꢀcosb¦1U12bbꢀccꢀcos aŁ

2393
Y[ Wu et al[
Table 5[ Re_ned Thermal Parameters "U|s# for 0!C5H3"CO#1NCH1!1! C5H4CH1OCH1CH1!0\ 1!C1B09H09 "4#2
Atom
U00
U11
U22
U12
U02
U01
O12
O13
O16
N03
C0
9[9527"7#
9[9796"8#
9[9414"6#
9[9381"7#
9[9343"8#
9[9436"09#
9[9356"8#
9[9392"8#
9[9307"8#
9[9535"01#
9[9641"03#
9[9576"02#
9[9469"00#
9[9314"8#
9[9362"8#
9[9698"01#
9[9605"02#
9[9449"03#
9[9339"09#
9[967"1#
9[9381"6#
9[9349"6#
9[9372"6#
9[9255"6#
9[9390"8#
9[9390"8#
9[9327"8#
9[9283"8#
9[9330"8#
9[9363"00#
9[9553"03#
9[975"1#
9[9694"02#
9[9384"09#
9[9308"8#
9[9316"09#
9[9279"09#
9[012"1#
9[9391"6#
9[9317"7#
9[9579"8#
9[9228"7#
9[9287"09#
9[9318"09#
9[9306"09#
9[9395"09#
9[9373"00#
9[964"1#
9[9966"5#
9[9963"5#
9[9147"5#
9[9016"5#
9[9044"6#
9[9041"6#
9[9190"6#
9[9012"6#
9[9087"7#
9[9121"09#
9[9379"03#
9[9467"03#
9[9212"09#
9[9114"7#
9[9013"6#
9[9958"7#
9[9020"7#
9[010"2#
9[9242"00#
9[9129"01#
9[001"2#
9[040"3#
9[931"1#
9[9115"02#
9[9196"8#
9[9104"8#
9[9050"7#
9[9035"7#
9[9157"00#
9[9166"09#
9[9176"09#
9[9189"00#
9[9229"00#
9[9304"02#
9[9030"5#
9[9031"5#
9[9969"5#
9[9003"5#
9[9032"6#
9[9069"7#
9[9024"6#
9[9989"6#
9[9014"6#
9[9110"09#
9[9258"02#
9[9265"01#
9[9114"8#
9[9028"6#
9[9093"6#
9[9025"8#
9[9950"09#
9[913"1#
9[9929"5#
9[9928"5#
−9[9957"5#
9[9908"5#
9[9934"6#
9[9982"6#
9[9949"6#
9[9935"6#
9[9943"6#
−9[9996"8#
9[9947"00#
9[9192"00#
9[9072"8#
9[9003"6#
9[9964"6#
9[9976"8#
−9[9949"8#
−9[9996"03#
−9[9043"8#
−9[9257"03#
−9[952"1#
9[903"1#
C1
C02
C04
C05
C06
C07
C08
C19
C10
C11
C14
C15
C17
C18
C29
C20
C21
C22
C23
B2
B3
B4
B5
B6
B7
B8
B09
B00
B01
9[090"1#
9[973"1#
9[9408"01#
9[9312"09#
9[9257"8#
9[9321"00#
9[9472"02#
9[103"3#
9[9695"03#
9[9479"03#
9[098"2#
9[9561"02#
9[982"1#
9[194"3#
9[052"3#
9[966"1#
9[9923"8#
9[9953"01#
−9[927"1#
9[923"1#
9[961"1#
9[934"1#
9[097"2#
9[977"1#
9[148"5#
9[061"3#
9[972"2#
9[996"1#
9[989"1#
9[9457"03#
9[9499"02#
9[9307"01#
9[9275"00#
9[9282"00#
9[9477"03#
9[9423"03#
9[9451"03#
9[9436"03#
9[950"1#
9[9946"01#
9[9053"09#
9[9000"8#
9[9976"7#
9[9037"7#
9[9103"00#
9[9114"09#
9[9970"8#
9[9920"09#
9[9012"00#
9[9051"00#
−9[931"1#
9[9964"8#
9[9925"8#
9[9994"8#
9[9922"7#
9[9086"09#
9[9028"09#
−9[9993"8#
−9[9906"09#
9[9006"09#
9[9012"00#
9[9598"01#
9[9598"01#
9[9434"00#
9[9407"00#
9[9480"02#
9[9410"01#
9[9358"00#
9[9457"02#
9[9466"02#
9[9363"01#
9[9311"00#
9[9367"00#
9[9310"00#
9[9274"09#
9[9469"02#
9[9471"02#
9[9458"02#
9[9477"02#
9[9477"02#
9[963"1#
9[960"1#
The form of the anisotropic displacement parameter is] expð−1p1"aꢀ1U00h1¦bꢀ1U11k1¦cꢀ1U22l1¦1bꢀcꢀU12kl¦
1aꢀcꢀU02hl¦1aꢀbꢀU01hk#Ł[

Synthesis and characterization of a protected amino alcohol containing ortho!carborane
2394
Ä
Table 6[ Bond Distances in Compound 0!C5H3"CO#1NCH1!1!C5H4CH1OCH1CH1!0\ 1!C1B09H09 "4#\ A
O12ÐC04
O16ÐC15
N03ÐC02
C0ÐB4
C0ÐB7
C1ÐB6
C02ÐH02a
C05ÐC06
C06ÐH06
C08ÐC19
C19ÐH19
C14ÐH14a
C15ÐH15b
C17ÐH17b
C29ÐC20
C20ÐH20
C22ÐC23
B2ÐB6
B2ÐB5
B3ÐB4
B3ÐH3
B4ÐB5
B6ÐB00
B6ÐH6
B7ÐH7
B8ÐH8
B09ÐH09
B01ÐH01
0[198"1#
0[310"1#
0[341"1#
0[696"2#
0[616"1#
0[600"2#
9[86
0[272"2#
9[82
0[278"2#
9[82
9[86
9[86
9[86
0[267"4#
9[82
0[234"3#
0[661"2#
0[668"2#
0[664"2#
0[98"1#
0[665"2#
0[654"2#
0[09"1#
0[97"1#
0[00"1#
0[00"1#
0[00"1#
O13ÐC11
N03ÐC11
C0ÐC02
C0ÐB8
C1ÐC14
C1ÐB7
C02ÐH02b
C05ÐC10
C07ÐC08
C08ÐH08
C10ÐC11
C14ÐH14b
C17ÐC18
C18ÐC29
C29ÐH29
C21ÐC22
C22ÐH22
B2ÐB00
B2ÐH2
B3ÐB00
B4ÐB09
B4ÐH4
B6ÐB01
B7ÐB01
B8ÐB01
B09ÐB00
B00ÐB01
0[100"1#
0[284"1#
0[417"1#
0[698"2#
0[416"2#
0[611"2#
9[86
0[276"1#
0[267"3#
9[82
0[375"1#
9[86
0[377"2#
0[253"2#
9[82
O16ÐC17
N03ÐC04
C0ÐC1
C0ÐB5
C1ÐB2
0[302"2#
0[288"1#
0[573"1#
0[611"1#
0[695"2#
0[621"1#
0[373"1#
0[272"2#
9[82
C1ÐB5
C04ÐC05
C06ÐC07
C07ÐH07
C19ÐC10
C14ÐC15
C15ÐH15a
C17ÐH17a
C18ÐC23
C20ÐC21
C21ÐH21
C23ÐH23
B2ÐB3
B3ÐB5
B3ÐB09
B4ÐB8
B5ÐH5
B6ÐB7
0[271"1#
0[494"2#
9[86
9[86
0[258"2#
0[256"5#
9[82
0[230"5#
9[82
9[82
0[662"2#
0[00"1#
0[668"2#
0[655"2#
0[09"1#
0[655"3#
0[669"2#
0[662"2#
0[665"2#
0[676"2#
0[663"2#
0[656"2#
0[671"2#
0[661"2#
0[97"1#
0[661"2#
0[666"2#
0[668"2#
0[673"3#
0[97"1#
B7ÐB8
B8ÐB09
B09ÐB01
B00ÐH00

2395
Y[ Wu et al[
Table 7[ Bond Angles in 0!C5H3"CO#1NCH1!1!C5H4CH1OCH1CH1!0\ 1!C1B09H09 "4#\ A
Ä
C17ÐO16ÐC15
C04ÐN03ÐC02
C1ÐC0ÐB4
B4ÐC0ÐB8
B4ÐC0ÐB5
C1ÐC0ÐB7
B5ÐC0ÐB7
C0ÐC1ÐB2
B2ÐC1ÐB6
000[3"1#
012[43"02#
009[47"02#
51[40"01#
51[39"00#
59[53"00#
002[06"02#
009[06"02#
51[35"01#
002[6"1#
59[40"09#
001[76"03#
097[55"7#
096[5
094[78"03#
097[1"1#
010[30"01#
008[07"03#
008[28"02#
010[24"02#
097[1"1#
094[78"03#
096[88"8#
096[1
C11ÐN03ÐC04
C02ÐC0ÐC1
C02ÐC0ÐB8
C02ÐC0ÐB5
B8ÐC0ÐB5
000[68"02#
007[63"03#
012[05"03#
002[61"02#
002[78"03#
002[43"03#
019[64"03#
007[4"1#
C11ÐN03ÐC02
C02ÐC0ÐB4
C1ÐC0ÐB8
C1ÐC0ÐB5
C02ÐC0ÐB7
B8ÐC0ÐB7
C14ÐC1ÐB2
C0ÐC1ÐB6
C0ÐC1ÐB7
C14ÐC1ÐB5
B6ÐC1ÐB5
N03ÐC02ÐH02a
C0ÐC02ÐH02b
O12ÐC04ÐC05
C06ÐC05ÐC04
C07ÐC06ÐH06
C08ÐC07ÐH07
C07ÐC08ÐH08
C10ÐC19ÐH19
C19ÐC10ÐC11
O13ÐC11ÐC10
C15ÐC14ÐH14a
C1ÐC14ÐH14b
O16ÐC15ÐH15a
C14ÐC15ÐH15b
O16ÐC17ÐH17a
C18ÐC17ÐH17b
C29ÐC18ÐC17
C18ÐC29ÐH29
C21ÐC20ÐH20
C22ÐC21ÐH21
C21ÐC22ÐH22
C22ÐC23ÐH23
C1ÐB2ÐB00
B6ÐB2ÐB3
B6ÐB2ÐB5
C1ÐB2ÐH2
B3ÐB2ÐH2
B5ÐB3ÐB4
B2ÐB3ÐB00
B2ÐB3ÐB09
B5ÐB3ÐH3
B00ÐB3ÐH3
C0ÐB4ÐB8
B09ÐB4ÐB3
B09ÐB4ÐB5
C0ÐB4ÐH4
B3ÐB4ÐH4
C0ÐB5ÐB3
C1ÐB5ÐB4
C1ÐB5ÐB2
C0ÐB5ÐH5
B4ÐB5ÐH5
C1ÐB6ÐB01
B00ÐB6ÐB2
B00ÐB6ÐB7
C1ÐB6ÐH6
012[77"03#
007[58"02#
009[32"02#
50[03"09#
010[00"03#
51[21"02#
010[0"1#
009[99"03#
59[81"09#
019[5"1#
B4ÐC0ÐB7
C14ÐC1ÐC0
C14ÐC1ÐB6
C14ÐC1ÐB7
B6ÐC1ÐB7
004[6"1#
B2ÐC1ÐB7
C0ÐC1ÐB5
B7ÐC1ÐB5
51[05"01#
51[20"00#
003[39"02#
097[55"8#
013[6"1#
010[3"1#
006[1"1#
010[5"1#
010[1"1#
006[2"1#
010[1"1#
013[6"1#
006[1"1#
096[88"00#
097[8"1#
098[89"09#
098[8"1#
098[6"1#
007[5"1#
B2ÐC1ÐB5
002[2"1#
N03ÐC02ÐC0
N03ÐC02ÐH02b
O12ÐC04ÐN03
C06ÐC05ÐC10
C07ÐC06ÐC05
C08ÐC07ÐC06
C07ÐC08ÐC19
C10ÐC19ÐC08
C19ÐC10ÐC05
O13ÐC11ÐN03
C15ÐC14ÐC1
C15ÐC14ÐH14b
O16ÐC15ÐC14
O16ÐC15ÐH15b
O16ÐC17ÐC18
O16ÐC17ÐH17b
C29ÐC18ÐC23
C18ÐC29ÐC20
C21ÐC20ÐC29
C22ÐC21ÐC20
C21ÐC22ÐC23
C22ÐC23ÐC18
C1ÐB2ÐB6
C1ÐB2ÐB3
C1ÐB2ÐB5
B3ÐB2ÐB5
B00ÐB2ÐH2
B5ÐB3ÐB2
B5ÐB3ÐB00
B5ÐB3ÐB09
B00ÐB3ÐB09
B4ÐB3ÐH3
C0ÐB4ÐB09
C0ÐB4ÐB3
C0ÐB4ÐB5
B3ÐB4ÐB5
B8ÐB4ÐH4
C0ÐB5ÐC1
C0ÐB5ÐB4
C0ÐB5ÐB2
B4ÐB5ÐB2
B3ÐB5ÐH5
C1ÐB6ÐB00
C1ÐB6ÐB2
C1ÐB6ÐB7
B2ÐB6ÐB7
B01ÐB6ÐH6
C1ÐB7ÐC0
C1ÐB7ÐB6
C1ÐB7ÐB8
B6ÐB7ÐB8
B01ÐB7ÐH7
097[55"7#
097[55"8#
018[3"1#
C0ÐC02ÐH02a
H02aÐC02ÐH02b
N03ÐC04ÐC05
C10ÐC05ÐC04
C05ÐC06ÐH06
C06ÐC07ÐH07
C19ÐC08ÐH08
C08ÐC19ÐH19
C05ÐC10ÐC11
N03ÐC11ÐC10
C1ÐC14ÐH14a
H14aÐC14ÐH14b
C14ÐC15ÐH15a
H15aÐC15ÐH15b
C18ÐC17ÐH17a
H17aÐC17ÐH17a
C23ÐC18ÐC17
C20ÐC29ÐH29
C29ÐC20ÐH20
C20ÐC21ÐH21
C23ÐC22ÐH22
C18ÐC23ÐH23
B6ÐB2ÐB00
B00ÐB2ÐB3
B00ÐB2ÐB5
B6ÐB2ÐH2
029[3"1#
010[30"03#
008[07"01#
008[28"01#
010[24"01#
029[5"1#
018[3"1#
096[88"09#
096[88"09#
098[89"09#
098[89"09#
098[6"1#
098[6"1#
019[6"2#
019[0"1#
019[1"2#
008[7"2#
019[9"2#
008[1"1#
094[3"1#
098[89"00#
097[2
098[6"1#
097[1
019[6"2#
019[0"1#
019[1"1#
008[7"2#
019[9"1#
008[1"1#
48[61"02#
59[19"02#
096[8"1#
010[4"09#
006[1"09#
097[9"1#
096[4"1#
48[42"01#
019[8"09#
012[6"09#
59[27"01#
097[5"1#
097[1"1#
018[3"8#
006[3"8#
093[81"03#
59[03"01#
59[92"01#
007[0"8#
015[1"8#
59[70"03#
097[7"1#
59[93"02#
029[1"00#
004[6"00#
093[8"1#
48[70"02#
48[87"02#
006[9"09#
008[7"2#
008[5"2#
019[3"2#
019[9"2#
010[5"2#
47[80"00#
094[65"03#
48[46"00#
48[54"01#
017[6"09#
59[21"00#
097[1"1#
096[82"03#
48[72"02#
010[4"09#
094[5"1#
094[32"03#
48[19"00#
48[56"01#
008[2"8#
47[23"09#
47[28"09#
094[00"02#
096[7"1#
096[8"1#
097[06"03#
006[3"09#
014[7"09#
59[08"00#
48[78"02#
096[6"1#
008[3"09#
012[3"09#
47[68"00#
59[32"01#
097[1"1#
004[4"8#
017[0"8#
094[07"03#
094[19"03#
47[01"00#
005[9"8#
B5ÐB2ÐH2
B2ÐB3ÐB4
B4ÐB3ÐB00
B4ÐB3ÐB09
B2ÐB3ÐH3
B09ÐB3ÐH3
B09ÐB4ÐB8
B8ÐB4ÐB3
B8ÐB4ÐB5
B09ÐB4ÐH4
B5ÐB4ÐH4
C1ÐB5ÐB3
B3ÐB5ÐB4
B3ÐB5ÐB2
C1ÐB5ÐH5
020[2"8#
094[5"1#
011[5"8#
094[8"1#
B2ÐB5ÐH5
B00ÐB6ÐB01
B01ÐB6ÐB2
B01ÐB6ÐB7
B00ÐB6ÐH6
B7ÐB6ÐH6
C0ÐB7ÐB01
B01ÐB7ÐB6
B01ÐB7ÐB8
C0ÐB7ÐH7
47[52"01#
48[12"00#
097[03"03#
015[1"00#
47[33"09#
47[50"01#
094[41"03#
096[5"1#
59[08"02#
097[6"1#
004[7"00#
010[1"00#
094[1"1#
094[14"03#
47[24"00#
005[8"00#
013[6"09#
B2ÐB6ÐH6
C1ÐB7ÐB01
C0ÐB7ÐB6
C0ÐB7ÐB8
C1ÐB7ÐH7
020[2"09#
B6ÐB7ÐH7
"continued on next pa`e#

Synthesis and characterization of a protected amino alcohol containing ortho!carborane
2396
Table 7 "continued#
B8ÐB7ÐH7
013[0"09#
097[9"1#
C0ÐB8ÐB4
C0ÐB8ÐB7
47[69"00#
48[23"00#
094[9"1#
096[8"1#
015[4"09#
097[0"1#
59[93"01#
096[7"1#
097[0"1#
010[3"00#
59[98"02#
097[9"1#
48[52"03#
097[0"1#
013[4"00#
59[04"02#
096[3"1#
48[46"03#
48[55"02#
010[8"00#
C0ÐB8ÐB01
B4ÐB8ÐB7
B4ÐB8ÐB09
C0ÐB8ÐH8
094[5"1#
097[9"1#
B4ÐB8ÐB01
B01ÐB8ÐB7
B01ÐB8ÐB09
B4ÐB8ÐH8
48[70"02#
59[17"02#
019[8"09#
018[0"00#
097[9"1#
C0ÐB8ÐB09
B7ÐB8ÐB09
B01ÐB8ÐH8
B4ÐB09ÐB00
B4ÐB09ÐB3
B4ÐB09ÐB01
B3ÐB09ÐB01
B8ÐB09ÐH09
B6ÐB00ÐB2
B6ÐB00ÐB3
B6ÐB00ÐB01
B3ÐB00ÐB01
B09ÐB00ÐH00
B6ÐB01ÐB7
B6ÐB01ÐB09
B6ÐB01ÐB00
B09ÐB01ÐB00
B8ÐB01ÐH01
48[53"01#
006[0"00#
006[2"00#
48[87"01#
48[88"02#
59[15"03#
010[8"00#
011[1"00#
096[7"1#
48[80"01#
096[7"1#
008[3"00#
011[6"00#
097[0"1#
B7ÐB8ÐH8
B09ÐB8ÐH8
B00ÐB09ÐB8
B8ÐB09ÐB3
B8ÐB09ÐB01
B00ÐB09ÐH09
B01ÐB09ÐH09
B2ÐB00ÐB09
B09ÐB00ÐB3
B09ÐB00ÐB01
B2ÐB00ÐH00
B01ÐB00ÐH00
B7ÐB01ÐB8
B8ÐB01ÐB09
B8ÐB01ÐB00
B7ÐB01ÐH01
B00ÐB01ÐH01
B4ÐB09ÐB8
B00ÐB09ÐB3
B00ÐB09ÐB01
B4ÐB09ÐH09
B3ÐB09ÐH09
B6ÐB00ÐB09
B2ÐB00ÐB3
B2ÐB00ÐB01
B6ÐB00ÐH00
B3ÐB00ÐH00
B6ÐB01ÐB8
B7ÐB01ÐB09
B7ÐB01ÐB00
B6ÐB01ÐH01
B09ÐB01ÐH01
097[9"1#
48[69"02#
010[7"00#
010[2"00#
097[9"1#
59[07"02#
59[97"03#
008[5"00#
011[3"00#
59[11"01#
59[92"02#
096[7"1#
097[9"1#
096[7"1#
008[6"00#
014[0"00#
007[6"00#
012[5"00#