Adducts of thianthrene- and phenoxathiin cation radical tetrafluoroborates to 1-alkynes. Structures and formation of 1-(5-thianthreniumyl)- and 1-(10-phenoxathiiniumyl)alkynes on alumina leading to α-ketoylides and α-ketols

Article abstract of DOI:10.1021/jo051317q

Thianthrene cation radical tetrafluoroborate (Th^.+BF ₄^-) added to the terminal alkynes 1-pentyne, 1-hexyne, 1-heptyne, 1-octyne, 1-nonyne, and 1-decyne to form trans-1,2-bis(5- thianthreniumyl)-alkene tetrafluoroborates (1-6). Similarly, addition of phenoxathiin cation radical tetrafluoroborate (PO^.+BF ₄^-) to the same alkynes gave 1,2-bis(10-phenoxathiiniumyl) alkene tetrafluoroborates (7-12). The trans configuration of two of the adducts (1 and 4) was shown with X-ray crystallography. When solutions of 1-6 in chloroform were stirred with activated alumina, cis elimination of a proton and thianthrene (Th) occurred with the formation of 1-(5-thianthreniumyl)alkyne tetrafluoroborates (1a-6a). Similar treatment of 8-12 caused elimination of a proton and phenoxathiin (PO) with formation of 1-(10-phenoxathiiniumyl)alkene tetrafluoroborates (8a-12a). Stirring of 1a-6a with alumina for short periods of time caused their conversion into 5-[(α-keto)alkyl]thianthrenium ylides (1b-6b) and α-ketols, RC(O)CH₂OH (1c-6c).

Full text of DOI:10.1021/jo051317q

Adducts of Thianthrene- and Phenoxathiin Cation Radical
Tetrafluoroborates to 1-Alkynes. Structures and Formation of
1
-(5-Thianthreniumyl)- and 1-(10-Phenoxathiiniumyl)alkynes on
Alumina Leading to r-Ketoylides and r-Ketols
†
,†
†
‡
Paramashivappa Rangappa, Henry J. Shine,* John N. Marx, Teyeb Ould-Ely,
‡
‡
Anna T. Kelly, and Kenton H. Whitmire
Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas 79409, and
Department of Chemistry, Rice University, Houston, Texas 77005
henry.shine@ttu.edu
Received June 27, 2005
•
+
-) added to the terminal alkynes 1-pentyne,
4
Thianthrene cation radical tetrafluoroborate (Th BF
-hexyne, 1-heptyne, 1-octyne, 1-nonyne, and 1-decyne to form trans-1,2-bis(5-thianthreniumyl)-
1
alkene tetrafluoroborates (1-6). Similarly, addition of phenoxathiin cation radical tetrafluoroborate
•
+
-
(
1
4
PO BF ) to the same alkynes gave 1,2-bis(10-phenoxathiiniumyl)alkene tetrafluoroborates (7-
2). The trans configuration of two of the adducts (1 and 4) was shown with X-ray crystallography.
When solutions of 1-6 in chloroform were stirred with activated alumina, cis elimination of a proton
and thianthrene (Th) occurred with the formation of 1-(5-thianthreniumyl)alkyne tetrafluoroborates
(
1a-6a). Similar treatment of 8-12 caused elimination of a proton and phenoxathiin (PO) with
formation of 1-(10-phenoxathiiniumyl)alkene tetrafluoroborates (8a-12a). Stirring of 1a-6a with
alumina for short periods of time caused their conversion into 5-[(R-keto)alkyl]thianthrenium ylides
(
1b-6b) and R-ketols, RC(O)CH OH (1c-6c).
2
Introduction
SCHEME 1
Recently, we have reported that addition of thian-
threne- and phenoxathiin cation radical tetrafluorobo-
•
+
-
•+
-
rates (Th BF
4
and PO BF
4
) to symmetrical alkynes
1
gave trans bisadducts. When these adducts were treated
with alumina in chloroform or acetonitrile solution,
complete loss of the heterocycle (Th or PO) occurred.
Cumulenes were formed and subsequently were con-
verted in situ into R-diketones, R-hydroxyalkynes, and
R-acetamidoalkynes. In continuation of our work with
alkynes we have found that addition of Th and PO to
terminal alkynes gives 1,2-bisadducts, also with trans
configurations. The chemistry of the 1,2-bisadducts on
alumina is quite dissimilar to that of symmetrical alkyne
adducts. We report here the formation and configuration
of the 1,2-bisadducts and their reactions on alumina.
Results and Discussion
•+
-
Structure of Adducts 1-12. Reaction of Th BF
4
•
+
•+
•+
-
and PO BF
4
with all alkynes readily gave 1,2-bisaducts
(1-12, Scheme 1). In all of these reactions only a
2
,3
bisadduct was formed; no evidence for monoadduct
formation was found. Crystals of 1 and 4 were grown
successfully for X-ray crystallography, which confirmed
their trans configuration. Only the ORTEP diagram of 4
(
2) Qian, D.-Q.; Shine, H. J.; Guzman-Jimenez, I. Y.; Whitmire, K.
†
Texas Tech University.
H. J. Org. Chem. 2002, 67, 4030-4039.
‡
Rice University.
(3) Shine, H. J.; Zhao, B.; Qian, D.-Q.; Marx, J. N.; Guzman-Jimenez,
I. Y.; Thurston, J. H.; Ould-Ely, T.; Whitmire, K. H. J. Org. Chem.
2003, 68, 8910-8917.
(
1) Shine, H. J.; Rangappa, P.; Marx, J. N.; Shelly, D. C.; Ould-Ely,
T.; Whitmire, K. H. J. Org. Chem. 2005, 70, 3877-3883.
10.1021/jo051317q CCC: $30.25 © 2005 American Chemical Society
9764
J. Org. Chem. 2005, 70, 9764-9770
Published on Web 10/22/2005

Formation of R-Ketoylides and R-Ketols
TABLE 2. 3C NMR Dataa for 7-12
1
chemical shifts (ppm)
assignment
7
8
9
10
11
12
+
PO quat
153.6
153.5
153.3
139.3
138.8
133.4
132.4
130.3
128.8
128.5
153.6
153.5
153.4
139.3
138.8
133.4
132.4
130.4
128.8
128.5
153.6
153.5
153.4
139.4
138.8
133.4
132.4
130.6
128.6
128.5
153.6
153.5
153.4
139.4
138.8
133.4
132.4
130.6
128.8
128.5
153.6
153.5
153.4
139.4
138.9
133.4
132.4
130.1
128.8
128.5
153.6
153.5
153.4
139.3
138.8
133.4
132.4
130.6
128.8
128.5
+
PO quat
C2
+
PO CH
+
PO CH
+
PO CH
+
PO CH
C1
+
PO CH
+
PO CH
+
PO CH
121.83 121.83 121.84 121.84 121.87 121.83
121.76 121.77 121.79 121.79 121.83 121.80
104.4
102.1
+
PO CH
+
PO quat
104.4
102.1
31.9
104.5
102.0
32.1
31.3
29.7
22.7
104.5
102.0
31.7
31.4
30.0
29.7
23.0
104.5
102.0
32.2
31.4
30.1
30.0
29.2
23.2
105.0
102.0
32.4
31.4
30.0
29.9
29.7
29.5
23.3
14.4
+
PO quat
3
2
1
2.9
3.7
4.1
31.0
FIGURE 1. ORTEP diagram for 1,2-bis(5-thianthreniumyl)-
23.3
1
-octene ditetrafluroborate (4). The counterions and solvent
13.5
of crystallization are omitted.
14.1
14.2
TABLE 1. 3C NMR Dataa for 1-6
1
14.4
chemical shifts (ppm)
a
assignment
C2
1
2
3
4
5
6
The last peak in each column is for the terminal CH3 group.
All other unassigned peaks are for CH2 groups.
148.5 148.7 148.7 148.7 148.7 148.7
138.2 138.2 138.2 138.2 138.2 138.2
137.1 137.1 137.1 137.1 137.1 137.1
137.0 137.0 137.0 137.0 137.0 137.0
136.9 136.9 136.9 136.9 136.9 136.9
136.6 136.5 136.5 136.5 136.5 136.5
134.9 134.9 134.9 134.9 134.9 134.9
131.9 131.9 131.9 131.9 131.9 131.9
131.7 131.7 131.7 131.7 131.7 131.7
131.5 131.5 131.5 131.5 131.5 131.5
131.4 131.4 131.4 131.4 131.4 131.4
121.2 121.2 121.2 121.2 121.2 121.2
119.6 119.7 119.7 119.7 119.7 119.7
116.6 116.7 116.7 116.7 116.7 116.7
+
Th quat
+
Th CH
+
Th CH
+
Th quat
+
Th CH
+
Th CH
+
Th CH
+
Th CH
+
Th CH
+
Th CH
C1
+
Th quat
+
Th quat
3
2
1
3.2
2.0
3.6
31.5
30.2
22.9
31.7
31.7
28.0
22.7
31.8
31.7
29.2
28.2
23.1
32.2
31.8
29.5
29.2
28.3
23.2
32.4
31.8
29.7
29.6
29.5
28.3
23.3
FIGURE 2. ORTEP diagram for 1-(5-thianthreniumyl)-1-
decyne tetrafluroborate (6a).
13.5
SCHEME 2
14.1
14.2
14.3
14.4
a
The last peak in each column is for the terminal CH3 group.
All other unassigned peaks are for CH2 groups.
is shown (Figure 1). The ORTEP diagram of 1 is to be
found in Supporting Information.
We deduce that the other adducts have the same
configuration on the basis of the uniformity and consis-
tency in their NMR data. For clarity of presentation
pertinent NMR data are given in tabular form. The 13
C
data for 1-6 (Table 1) and 7-12 (Table 2) show uniformly
eight aromatic CH, four aromatic quaternary C atoms,
the CH and quaternary C of the alkene, and the relevant
+
(or PO ) units were eliminated. This behavior differs from
that of adducts of symmetrical alkynes from which all of
the heterocycle was eliminated. Eliminations from 1-6
1
CH
2
and CH
3
carbons
1
The aromatic H NMR spectra of 1-12 were made
complex by overlapping multiplets. The spectra were, for
the most part, consistent in their complexity within each
series and were in agreement with the structures of the
gave the terminally substituted alkynes 1a-6a, and
8-12 gave 8a-12a. It is evident from the structures of
1-12 that cis elimination occurred in the formation of
1a-12a (Scheme 2).
The structure of 6a was confirmed with X-ray crystal-
lography (Figure 2). The structures of the remaining
products were deduced with detailed NMR studies,
pertinent data of which are given in tabular form. The
1
adducts. The H NMR data have not been presented in
tabular form. Satisfactory elemental analyses were ob-
tained for 2, 4, 5, 6 and 8.
Reactions of 1-12 on Alumina. When solutions of
+
1
adducts were stirred with alumina, one-half of the Th
aromatic H data for 1a-6a (Table 3) and 8a-12a (Table
J. Org. Chem, Vol. 70, No. 24, 2005 9765

Rangappa et al.
TABLE 3. 1H NMR Data for Aromatic Protons in 1a-6a
chemical shifts (ppm) and coupling (Hz)
multiplicity
1a
2a
3aa
4a
5a
6a
dd, 2H
dd, 2H
td, 2H
td, 2H
8.48 (8.3, 1.3)
7.89 (7.8, 1.3)
7.75 (7.7, 1.2)
7.67 (7.5, 1.0)
8.48 (8.0, 1.0)
7.90 (8.0, 1.0)
7.76 (7.8, 1.3)
7.68 (7.8, 1.3)
8.49 (8.0)
7.89 (7.5)
7.75 (7.5)
7.68 (7.5)
8.48 (8.0, 1.0)
7.90 (8.0, 1.0)
7.76 (7.7, 1.2)
7.68 (7.5, 0.5)
8.49 (8.0, 1.0)
7.90 (7.5, 1.3)
7.76 (7.7, 1.3)
7.68 (7.9, 1.2)
8.46 (8.0, 1.0)
7.90 (8.0, 1.0)
7.77 (7.8, 1.5)
7.67 (7.8, 1.0)
b
a
Resolved as only d and t. b Central peak of td is seen as overlapped dd.
TABLE 4. 1H NMR Data for Aromatic Protons in 8a-12a
chemical shifts (ppm) and coupling (Hz)
multiplicity
8a
9a
10a
11a
12a
dd, 2H
td, 2H
dd, 2H
td, 2H
8.23 (8.0, 1.5)
7.86 (7.3, 1.3)
7.63 (8.5, 1.0)
7.55 (7.3, 1.0)
8.23 (8.0, 1.0)
7.86 (8.0, 1.3)
7.64 (8.5, 1.0)
7.55 (8.0, 1.3)
8.23 (8.0, 1.5)
7.86 (8.0, 1.5)
7.64 (8.3, 0.8)
7.55 (7.8, 1.0)
8.27 (8.0, 1.5)
8.23 (8.0, 1.5)
7.86 (7.8, 1.5)
7.63 (8.5, 1.0)
7.55 (7.8, 1.5)
a
a
7.84 (7.3, 1.3)
7.61 (8.3, 1.3)
7.58 (7.0, 1.0)
a
a
Central peak of td is seen as overlapped dd.
TABLE 5. 13C NMR Data for Aromatic and Yne Carbon
TABLE 7. 1H NMR Data for Isomers of 2b
chemical shifts (ppm) and coupling (Hz)
Atoms in 1a-6a
chemical shifts (ppm)
multiplicity
(Z)-2b
7.75 (7.5)a
7.63 (7.3, 1.3)
7.48 (7.6, 1.3)
7.43 (7.5, 1.5)
3.97
(E)-2b
assignment
1a
2a
3a
4a
5a
6a
d
7.92 (8.0, 1.0)b
7.67 (7.5, 1.5)
7.54 (7.6, 1.2)
7.48 (7.5, 1.3)
3.95
+
Th quat
136.2 136.2 136.1 136.1 136.1 136.1
134.5 134.5 134.5 134.5 134.5 134.6
133.5 133.5 133.6 133.4 133.5 133.4
130.2 130.2 130.2 130.2 130.2 130.2
130.1 130.1 130.1 130.1 130.1 130.1
121.0 121.0 120.1 121.0 121.0 121.0
107.4 107.6 107.5 107.6 107.6 107.6
dd
+
Th CH
td
+
Th CH
td
+
Th CH
s
t
+
Th CH
2.50 (7.8)
1.79 (7.6)
2.47 (7.5)
+
c
1.66 (7.6)c
1.34 (7.6)
Th quat
quint
sext
t
yne
yne
1.44 (7.5)
0.99 (7.3)
54.6
54.4
54.5
54.4
54.6
54.4
0.86 (7.3)
a
The major signal was d. b The minor signal was dd. c Treated
as a quintet. In each multiplet the three central signals were
further split with shoulders suggestive of triplets.
TABLE 6. 13C NMR Data for Aromatic and Yne Carbon
Atoms in 8a-12a
chemical shifts (ppm)
product, was isolated in each case. Each ylide was found
with NMR spectroscopy to be a mixture of two compo-
nents in an approximate ratio of 5:1, deduced to be the
(Z)- and (E)-isomers. Many of the NMR signals from pairs
of isomers, particularly those with shorter carbon chains
assignment
8a
9a
10a
11a
12a
+
PO quat
152.6
136.9
131.4
127.4
120.4
107.5
110.7
59.9
152.6
136.9
131.4
127.4
120.3
107.5
110.7
59.9
152.6
136.9
131.3
127.4
120.4
107.5
110.7
59.9
152.6
136.8
131.7
127.5
120.2
107.8
110.6
60.0
152.6
136.9
131.4
127.4
120.3
107.5
110.7
59.9
+
PO CH
+
PO CH
+
PO CH
(
1b, 2b), were sufficiently well separated to enable their
+
PO CH
+
distinction. An example is given with 2b in Table 7. The
major isomer is assigned the (Z)-configuration. The data
show that the aromatic signals of the (Z)-assigned isomer
are upfield of those of the (E)-assigned isomer. The
reverse is true of the alkyl chain signals. Our reasoning
for these assignments is that in the (E)-isomer the alkyl
chain is shielded by the aromatic π-system and thus
resonates upfield. At the same time, the ylide’s singlet
proton is shielded by the nearness of the enolate oxygen
atom and also resonates upfield. In the (Z)-isomer the
aromatic protons are shielded by the enolate oxygen and
thus resonate upfield.
PO quat
yne
yne
4
) show uniformity throughout each series. The occur-
rence of two dd (from 1,9- and 4,6-protons) and two td
from 2,8- and 3,7-protons) in each series attests to the
symmetry of the sulfonium heterocycle in each compound.
(
13
+
This is confirmed with the C data for the Th (Table 5)
+
and PO (Table 6) rings, there being in each set of data
only four CH and two quaternary carbon atoms. The
1
difference in the sequences of the H dd and td multiplets
+
+
1
in the Th and PO series (Tables 3 and 4) has been
explained earlier. Satisfactory elemental analyses were
obtained for 1a, 3a, and 5a.
The consistency in the H NMR data for the major (Z)-
1
isomers of the four remaining ylides is shown in Table
8. Notably, the furthest downfield signal, which should
be a dd in each compound, was broadened into a d; the
Reactions of 1a-6a on Alumina. Formation of
R-Ketoylides and R-Ketols. A. Formation of R-Ke-
toylides. When a chloroform solution of a 1-(5-thian-
threniumyl)alkyne itself was stirred with alumina for
short periods of time, two products were formed: an
R-ketoylide and an R-ketol. This behavior was studied
with five of the terminally substituted alkynes: 1a, 2a,
and 4a-6a. The ylide (1b, 2b, 4b-6b), the major
1
3
reason is being sought. It was possible to assign the
C
signals for all carbon atoms in each of the five ylides,
and the data are listed in Table 9.
Although the two isomers of each ylide were seen
clearly in the NMR spectra, they could not be detected
separately by GC. Two ylides (2b and 4b) were charac-
terized with direct-insertion mass spectrometry. Satisfac-
9766 J. Org. Chem., Vol. 70, No. 24, 2005

Formation of R-Ketoylides and R-Ketols
TABLE 8. 1H NMR Data for the Aromatic Protons of the
were overlapped with signals from the ylide. The only
H signals that could be attributed with confidence to the
(
Z)-isomers
1
chemical shifts (ppm) and coupling (Hz)
R-ketol in a mixture were those from the terminal
methylene group, -CH OH, in the region of 4.2 ppm, and
2
multi-
plicity
1b
4b
5b
6b
the terminal methyl group in the region of 0.9 ppm, well-
separated from the ylide’s methyl group signal in the
region of 1.0 ppm. The 13C NMR data agreed well with
those of authentic 4c prepared by the oxidation of 1,2-
octane diol12 and reported data of 1c.
d, 2H 7.75 (7..5)
7.68 (8.0)
7.76 (7.5)
7.82 (7.5)
dd, 2H 7.62 (7.3, 1.3) 7.56 (7.5, 1.5) 7.63 (7.8, 1.3) 7.56 (7.3, 1.3)
td, 2H 7.46 (7.8, 1.5) 7.40 (7.5, 1.5) 7.47 (7.5, 1.5) 7.40 (7.5, 1.5)
td, 2H 7.42 (7.5, 1.5) 7.36 (7.5, 1.3) 7.43 (7.5, 1.5) 7.36 (7.5, 1.5)
13
We attribute the formation of ylides and R-ketols to
hydration reactions of 1a-6a on the alumina (Schemes
tory elemental analysis was obtained for 2b. Confirma-
tion of the nature of 2b was also obtained by protonation
3
and 4). The major hydration reaction (releasing a
4
with HBF -etherate, which converted 2b into 5-[(2-keto)-
proton) on the basic surface of the alumina led directly
to the ylide (Scheme 3). A small amount of the ylide
became protonated to give a â-ketosulfonium ion, which
underwent displacement of Th to give the R-ketol (Scheme
hexyl]thianthrenium tetrafluoroborate (2d), eq 1. The
4
). That only a small part of the ylide was protonated
may be attributed to the neutralizing, basic nature of the
alumina. The possibility of displacing Th from a 5-(ke-
toalkyl)thianthrenium ion on alumina was confirmed
with the use of 5-[(2-keto)-3-pentyl]thianthrenium tet-
rafluoroborate (13), from which 3-hydroxy-2-pentanone
formation of 5-[(â-keto)alkyl]thianthrenium perchlorates
•+
-
by reactions of ketones with Th ClO
4
was reported from
4-6
this laboratory about 30 years ago.
Reactions were
(
14) was obtained, eq 2.
7
•+
deduced then and later to occur by addition of Th to
the enolic form of the ketone. In those cases, reactions
with methyl ketones, MeC(O)R, in which the group R had
an enolizable H atom, e.g., 2-butanone, occurred neces-
sarily at that enolizable position rather than at the
methyl group. That means that formation of 2d, for
example, would not be possible by reaction of 2-hexanone
Two Classes of Adducts. Adducts of symmetrical
•
+
-
with Th BF
a and 2b is unique.
Ketosulfonium ylides have been described as being
4
. Consequently, the preparation of 2d via
1
alkynes and of the present terminal alkynes each have
the trans configuration. They differ in their reactions on
alumina in ways that are now clear. Symmetrical adducts
can readily undergo E2-type eliminations to give cumu-
lenes (eq 3), which continue on to give the observed
2
8
9
isolable compounds for about 40 years. Their cis/trans
enolate isomers were recognized quite early in that
period, and Trost10 suggested as early as 1967 that steric
and electrostatic factors favored a (Z)- over an (E)-isomer.
Our work with terminal alkyne adducts has led us
unexpectedly through an unconventional route into this
area of organic chemistry.
B. Formation of R-Ketols. The presence of a small
amount of an R-ketol (1c, 4c, and 6c) was detected with
NMR spectroscopy as a minor product in the isolated
crude mixture of products of reaction in three cases (1a,
1
products. Terminal alkynes can in principle undergo
elimination to give 1-(sulfoniumyl)allenes (eq 4), but the
4
a, and 6a). R-Ketol 6c was isolated and its structure
1
13
was confirmed by comparison of its H and C NMR
spectra with those of an authentic sample prepared by
the oxidation of 1,2-decanediol.11 The other two R-ketols
could not be isolated separately. Their structures were
deduced, however, from comparisons of their NMR
spectra discernible in the mixture with the corresponding
preferred elimination involves the more acidic terminal
proton (eq 5). Once that has happened, removal of the
1
3
ylide. That was more easily achieved with their
C
1
spectra than with their H spectra, most of whose signals
(
4) Kim, K.; Mani, S. R.; Shine, H. J. Tetrahedron Lett. 1974, 4413-
4
3
4
416.
(
5) Kim, K.; Mani, S. R.; Shine, H. J. J. Org. Chem. 1975, 40, 3857-
862.
(
6) Padilla, A. G.; Bandlish, B. K.; Shine, H. J. J. Org. Chem. 1977,
2, 1833-1836.
+
+
remaining sulfonium group (Th or PO in the present
cases) can only occur by an unlikely substitution reaction
at the alkynyl carbon atom; it cannot happen by elimina-
(
7) Houman, A.; Shukla, D.; Kraatz, H.-B.; Wayner, D. D. M. J. Org.
Chem. 1999, 64, 3342-3345.
8) Trost, B. M.; Melvin, L. S., Jr. Sulfur Ylides; Academic Press:
(
NewYork, 1975.
(
(
(
9) Ratts, K. W.; Yao, A. N. J. Org. Chem. 1966, 31, 1185-1188.
10) Trost, B. M. J. Am. Chem. Soc. 1967, 89, 138-142.
(12) Martin, S.; Garrone, A. Tetrahedron Lett. 2003, 549-552.
(13) Matsumoto, T.; Ohishi, M.; Onoue, S. J. Org. Chem. 1985, 50,
603-606.
11) Kanemoto, S.; Tomioka, H.; Oshima, K.; Nozaki, H. Bull. Chem.
Soc. Jpn. 1986, 59, 105-108.
J. Org. Chem, Vol. 70, No. 24, 2005 9767

Rangappa et al.
TABLE 9. 3C NMR Dataa for (Z)- and (E)-Isomers 1b-6b
1
chemical shifts (ppm)
1b
2b
4b
5b
6b
(
Z)
(E)
(Z)
(E)
(Z)
(E)
(Z)
(E)
(Z)
(E)
CO
193.0
132.5
131.9
130.1
129.4
128.4
125.8
194.5
134.8
131.7
130.5
129.7
128.9
125.6
b
193.2
132.6
131.9
130.1
129.5
128.4
125.8
49.7
194.8
134.9
131.8
130.5
129.7
129.0
125.7
b
193.1
132.6
131.9
130.1
129.5
128.4
125.8
49.7
194.8
134.8
131.8
130.4
129.7
128.9
125.7
b
36.2
31.7
29.3
27.6
22.5
14.0
193.1
132.6
132.0
130.1
129.5
128.4
125.9
49.8
194.8
134.8
131.8
130.4
129.7
128.9
125.7
b
36.2
31.7
29.6
29.1
27.7
22.6
14.0
193.2
132.6
132.0
130.1
129.5
128.4
125.9
49.7
194.8
134.9
131.8
130.5
129.7
128.9
125.7
b
36.2
31.8
29.6
29.4
29.2
27.6
22.6
14.0
+
T h quat
+
T h CH
+
T h CH
+
T h CH
+
T h CH
+
T h quat
49.9
43.8
20.6
14.3
38.2
41.6
36.0
41.8
41.8
41.9
20.9
14.1
29.5
29.8
31.8
31.9
31.9
22.9
22.8
29.5
29.8
29.9
14.0
13.9
27.3
29.3
29.6
2
1
2.6
4.1
27.4
29.4
22.1
27.4
14.1
22.7
14.1
a
The last peak listed in each column is for the terminal CH3. All other unassigned data are for CH2 groups. b Signal too small to be
seen.
SCHEME 3
mmol) were placed side by side in an argon-flushed 500 mL
round-bottom flask equipped with magnetic stirrer, rubber
septa, and argon bubbler. Then, 25 mL of acetonitrile was
injected through a septum. The solution, which turned blue
immediately, was stirred for 45 min, after which 0.69 g (10.1
mmol) of 1-pentyne was added through a septum. Stirring was
continued for 60 h, during which the color of the solution faded
to pale yellow. Dry ether (250 mL) was added, causing the
precipitation of a cream-colored solid; filtration and washing
with ether gave 850 mg (1.26 mmol, 48%) of 1, mp 229-230
°
C (dec). Single crystals were grown successfully for X-ray
crystallography. All other products were made with this
procedure; % yield and mp °C (dec): 2, 53, 213-214; 3, 51,
217-218; 4, 63, 220-222; 5, 50, 215-216; 6, 56, 200-201; 7,
82, 192-193; 8, 76, 186-188; 9, 76, 182-183; 10, 66, 177-
178; 11, 54, 149-150; 12, 29, 130-132.
Elemental Analyses. 2. Calcd for C30
H, 3.8; F, 22.1; S, 18.6. Found: C, 52.2; H, 3.7; F, 21.6; S, 18.5.
. Calcd for C32 : C, 53.6; H, 4.2; S, 17.9; F, 21.2.
Found. C, 53.5; H, 4.2; S, 18.0; F, 20.7. 5. Calcd for
: C, 54.6; H, 4.4; F 20.8; S, 17.3. Found: C, 54.5;
H, 4.3; F, 20.4; S, 17.3. 6. Calcd for C34 : C, 54.9; H,
.6; F 20.4; S, 17.2. Found: C, 55.2; H, 4.8; F, 20.3; S, 16.9. 8.
26 4 2 8
H S B F : C, 52.3;
4
30 4 2 8
H S B F
SCHEME 4
33 32 4 2 8
C H S B F
34 4 2 8
H S B F
4
2 8
Calcd for C30H26SOB F : C, 54.9; H, 4.0; S, 9.8; F, 23.2.
Found: C, 54.7; H, 3.8; S, 9.2; F, 23.
1
1
3
H NMR (500 MHz, CD CN). Only H data δ (J) are given
13
below; J data are averaged. C NMR data are listed in Tables
1
(
(
and 2. 1: 8.21 (8.0, 0.5), bd dd, 2H; 8.16 (7.8), bd d, 2H; 7.92
8.0, 1.0), dd, 2H; 7.90-7.88, m, 4H; 7.78-7.41, m, 2H; 7.85
7.8, 1.5), td, 2H; 7.72 (8.0, 1.5), dd, 1H overlapping 7.71 (8.0,
1
0
7
.5), dd, 1H; 6.36, s, 1H; 2.48 (7. 8), t, 2H; 1.48 (7.5) sext, 2H;
.93 (7.3), t, 3H. 2: 8.22 (8.3), bd d, 2H; 8.16 (8.0), bd d, 2H;
.92 (8.0, 1.0), dd, 2H; 7.89, m, 4H; 7.85 (7.8, 1.2), td, 2H; 7.77-
tion. Thus, the products 1a-12a are obtained in the
present work.
7.74, m, 2H; 7.71 (7.6, 1.2), td, 2H; 6.34, s, 1H; 2.50 (7.5), t,
2
2
7
H; 1.35-1.28, m, 4H; 0.84 (6.8), t, 3H. 3: 8.21 (8.0), bd d,
H; 8.16 (8.0, 1.0), dd, 2H; 7.92 (8.3, 1.3), dd, 2H; 7.89, m, 4H;
.85 (7.6, 1.2), td, 2H; 7.78-7.74, m, 2H; 7.71 (7.8, 0.8), td,
Experimental Section
Solvent acetonitrile was dried by distillation from P
2
O
5
.
2H; 6.33, s, 1H; 2.51 (8.0), t, 2H; 1.34-1.30, m, 2H; 1.27-1.26,
m, 4H; 0.86 (7.0), t, 3H. 4: 8.21 (8.0, 1.0), bd dd, 2H; 8.15 (8.0),
bd d, 2H; 7.92 (8.0, 1.5), dd, 2H; 7.89, m, 4H; 7.85 (7.8, 1.5),
td, 2H; 7.77-7.40, m, 2H; 7.71 (7.8, 1.0), td, 2H; 6.33, s, 1H;
2.51 (7.3), t, 2H; 1.34-1.30, m, 2H; 1.29-1.23, m, 4H; 1.20-
1.16, m, 2H; 0.89 (7.3), t, 3H. 5: 8.21 (8.5), bd d, 2H; 8.15 (8.0,
1.0), bd dd, 2H; 7.92 (8.0, 1.0), dd, 2H; 7.89, m, 4H; 7.85 (7.8,
1.3), td, 2H; 7.78-7.74, m, 2H; 7.71 (7.8, 0.8), td, 2H; 6.33, s,
1H; 2.51 (7.8), t, 2H; 1.93-1.33, m, 10H; 0.91 (7.3), t, 3H. 6:
8.21 (8.0), bd d, 2H; 8.15 (8.0, 1.0), dd, 2H; 7.92 (8.0,1.0), dd,
2H; 7.90-7.88, m, 4H; 7.85 (8.0, 1.5), td, 2H; 7.77-7.74, m,
Diethyl ether was dried over sodium. Alkynes were purchased
from commercial sources. NMR spectra were recorded in a 500
MHz instrument; coupling constants (J) are averaged where
necessary. DEPT, HMQC, HMBC, and COSY were used in
aiding identification of new compounds. Gas chromatography
(
GC) was carried out with an OV-101 column. X-ray crystal-
1
lographic data were recorded as described earlier. Activated
basic alumina was from the Aluminum Company of America.
Preparation of Adducts 1-12. An example is given with
1
. Thianthrene (1.00 g, 4.62 mmol) and NOBF
4
(0.610 g, 5.22
9768 J. Org. Chem., Vol. 70, No. 24, 2005

Formation of R-Ketoylides and R-Ketols
1
2
1
1
7
2
2
H; 7.71 (7.6, 1.2), td, 2H; 6.33, s, 1H; 2.51 (7.8), t, 2H; 1.34-
.16, m, 12H; 0.91 (7.3), t, 3H. 7: 7.96-7.90, m, 6H; 7.86 (8.0,
.5), dd, 2H; 7.67 (8.5, 1.5), dd, 2H; 7.60 (8.5, 1.0), dd, 2H; 7.58-
.54, m, 4H; 6.87, s, 1H; 2.72-2.69, m, 2H; 1.34 (7.4), sext,
H; 0.91 (7.3), t, 3H. 8: 7.96-7.91, m, 6H; 7.87 (8.0, 1.5), dd,
H; 7.67 (8.5, 1.0), dd, 2H; 7.60 (8.8, 1.3), dd, 2H; 7.56-7.55,
(CH
(7.3), quint, 2H; 1.23, m, 10H; 0.86, (7.3), t, 3H. C: 31.6 (CH
28.9, (CH ), 28.6 (2 CH ), 26.6 (CH ), 22.5 (CH ), 20.0 (CH
14.0 (CH ).
2 2 3
), 20.0 (CH ), 14.0 (CH ). 12a. H: 2.36 (7.3), t, 2H; 1.48
13
2
),
),
2
2
2
2
2
3
Reaction of 1a, 2a, and 4a-6a on Alumina. Isolation
of R-Ketothianthrene Ylides. Method A. A mixture of 0.450
g (1.22 mmol) of 1a and 50 mL of chloroform was stirred with
m, 4H; 6.93, s, 1H; 2.74-2.70, m, 2H; 1.31 (7.1), sext, 2H; 1.24-
1
1
.18, m, 2H; 0.82 (7.3), t, 3H. 9: 7.99-7.95, m, 4H; 7.92 (8.3,
1
1 g of alumina for 1 h at room temperature. The combined
.3), dd, 2H; 7.89 (8.0, 1.5), dd, 2H; 7.70 (8.0, 1.0), dd, 2H; 7.63
chloroform filtrate and washing (20 mL) was concentrated to
a small volume to which was added 5 mL of cold acetonitrile
to precipitate Th. The filtered MeCN solution was concentrated
under reduced pressure, and the residue was triturated three
times with warm hexane. The hexane solution (75 mL) was
concentrated to 10 mL, which at room temperature overnight
deposited 45 mg (0.166 mmol, 13%) of crystalline 1b, mp 129-
(
7.0, 1.0), dd, 2H; 7.61-7.57, m, 4H; 6.98, s, 1H; 2.75-2.72,
m, 2H; 1.28-1.21, m, 6H; 0.86 (7.0), t, 3H. 10: 7.99-7.95, m,
4
1
1
0
7
H; 7.92 (8.3, 1.3), dd, 2H; 7.88 (8.0, 1.5), dd, 2H; 7.70 (8.5,
.0), dd, 2H; 7.63, (8.0, 1.0), dd, 2H; 7.61-7.57, m, 4H; 6.99, s,
H; 2.75-2.71, m, 2H; 1.29-1.22, m, 6H; 1.21-1.16, m, 2H;
.91(7.3), t, 3H. 11: 7.97-7.92, m, 4H; 7.90 (8.0, 1.5), dt, 2H;
.86 (8.5, 1.3), dt, 2H; 7.68 (8.3, 1.3), dd, 2H; 7.60 (8.5, 1.3),
1
30 °C. The product was shown with NMR spectroscopy to
dd, 2H; 7.58-7.54, m, 4H; 6.98 (2.0), d, 1H; 2.72-2.69, m, 2H;
contain two components. Similar treatment of 2a gave 2b,
1.31-1.17, m, 10H; 0.91 (7.3), t, 3H. 12: 7.97-7.92, m, 4H;
7.90 (8.0, 1.0), dd, 2H; 7.86 (8.0, 1.5), dd, 2H; 7.68 (7.5), bd d,
2H; 7.60 (8.5), bd d, 2H; 7.58-7.54, m, 4H; 6.98, s, 1H; 2.72-
2.69, m, 2H; 1.34-1.29, m, 2H; 1.28-1.12, m, 10H; 0.91 (7.0),
1
9%, mp 109-110 °C; 5a gave 5b, 7%, 99-100 °C.
Method B. The same procedure was applied to 4a and 6a,
to obtain the residue from concentrating the MeCN solution
of product. Thereafter, the residue was dissolved in a small
amount of chloroform and loaded onto a column of activated
alumina. Elution with hexane containing 2% of ethyl acetate
removed Th. Elution with hexane containing 10% ethyl acetate
gave the ylide, which was recrystallized from hexane. In this
way was obtained 4b, 10%, mp 104-105 °C, and 6b, 10%, mp
t, 3H.
Preparation of 1a-6a and 8a-12a. An example is given
with 1-(5-thianthreniumyl)-1-pentyne tetrafluroborate (1a). In
a 100 mL flask were placed 850 mg (1.26 mmol) of 1, 3.4 g of
alumina, and 15 mL of chloroform. The suspension was stirred
for 2 h at room temperature and filtered. The alumina was
washed with 25 mL of chloroform, and the combined chloro-
form solution was concentrated under reduced pressure to
small volume, to which was added 75 mL of ether precooled
in ice. The precipitate was separated by filtration, washed with
ether, and dried under vacuum to give 350 mg (0.945 mmol,
78-79 °C.
3
NMR Spectra (500 MHz, CDCl ) for 1b, 2b, and 4b-
b. H and C spectra showed the presence of two components,
1
13
6
1
the (E)- (minor), and (Z)- (major) isomers. In the H spectra,
the downfield aromatic signals were well separated as dd. In
the upfield region there was some overlapping of two sets of
td. Nevertheless, in the upfield aromatic region the two major
td of the (Z)-isomer were clearly characterized. Therefore it
was possible to tabulate (Table 8) the major aromatic signals
of the five ylides. All of the minor isomer’s aromatic signals
were downfield from the corresponding major isomer’s signals.
75%) of 1a, mp 128-130 °C (dec). GC analysis of the etherate
filtrate gave 1.19 mmol (95%) of Th. Similar reactions were
carried with 2-6 and 8-12; % yield, mp °C (dec), and %Th or
PO: 2a, 83, 122-123, 94; 3a, 75, 69-70, 95; 4a, 71, 96-97,
98; 5a, 78, 125-126, 95; 6a, 75, 91-92, 96; 8a, 63, 98-99, 96;
9a, 53, 86-88, 97; 10a, 60, 115-116, 96; 11a, 39, 98-99, 92;
12a, 68, 83-84, 93.
1
Among the alkyl H signals it was possible to differentiate the
signals from the two CH (ylide) protons and the two terminal
Elemental Analyses. 1a. Calcd for C17
H, 4.08; S, 17.3. Found: C, 55.3; H, 4.07; S, 17.6. 3a. Calcd
for C19 BF : C, 57.3; H, 4.8; S, 16.1. Found: C, 57.0; H,
.1; S, 15.9. 5a. Calcd for C21 BF : C, 59.2; H, 5.40; S,
5.0. Found: C, 59.2; H, 5.45; S, 15.2.
NMR Data (500 MHz, CDCl ) for 1a-6a, 8a-12a. The
aromatic portions of the H data are listed in the Tables 3 and
15 2 4
H S BF : C, 55.2;
3
CH groups. Some other signals, particularly in the smaller
chains of 1b, 2b, were also reasonably well separated.
H
19
S
2
4
1
The aromatic H proton data δ (J) of (E)-isomers and all
5
1
H
23
S
2
4
other nontabulated data for 1b and 4b-6b are given below.
1
All H signals from the isomer 2b were sufficiently well
3
1
discernible that they are listed in Table 7 to show their
1
3
1
3
downfield-upfield relationship. The C signals of the two
isomers were clearly assignable based on peak height. They
are tabulated, for clear presentation, in Table 9. Two features
4
. The C data for aromatic and yne carbon atoms are listed
1
13
in the Tables 5 and 6. The remaining H, δ (J) and C data
1
are given below. J values are averaged. 1a. H: 2.34 (7.0), t,
1
13
1
3
of each H and C spectrum were noted. The most downfield
2
2
H; 1.54 (7.2), sext, 2H; 0.88 (7.3), t, 3H. C: 21.9 (CH ), 20.4
1
1
aromatic H signals in each (Z)-isomer were broadened into a
(
CH
2
), 13.3 (CH
3
). 2a. H: 2.37 (7.0), t, 2H; 1.50 (7.4), quint,
13
doublet instead of dd. The carbonyl carbon peak of each (Z)-
2
H; 1.28 (7.4), sext, 2H; 0.84 (7.3), t, 3H. C: 28.7(CH
2
), 21.9
1
isomer was also broadened.
(
CH
2 2 3
), 19.7 (CH ), 13.2 (CH ). 3a. H: 2.36 (7.0), t, 2H; 1.51
1
3
(Z)-1b: 4.0, s, 1H; 2.48 (7.8), t, 2H; 1.83 (7.5), sext, 2H.; 1.08
(7.3), t, 3H. (E)-1b: 7.90 (8.0, 1.5), dd, 2H; 7.66 (7,8, 1.3), dd,
2H; 7.53 (7.6, 1.3), td, 2H; 7.47, m, 2H overlapped with (Z)-
1b; 3.97, s, 1H; 2.45 (8.0), t, 2H, partly overlapped with (Z)-
1b; 1.70 (7.5), sext, 2H; 0.92 (7.5), t, 3H. (Z)-4b: 3.90, s, 1H;
2.43 (7.3), t, 2H; 1.73 (7.6), quint, 2H; 1.42-1.37, m, 2H; 1.32-
1.28, m, 4H; 0.86 (7.3), t, 3H. (E)-4b: 7.85 (8.0, 1.5), dd, 2H;
7.60 (7.8, 1.3), dd, 2H; 7.47 (7.6, 1.3), td, 2H; 7.42, m, 2H
overlapped with (Z)-4b; 3.89, s, 1H; 2.40 (7.5), t, 2H, partly
overlapped with (Z)-4b; 1.60 (7.4), quint, 2H; 0.73 (7.3), t, 3H;
other peaks were poorly defined. (Z)-5b: 3.97, s, 1H; 2.50 (7.5),
t, 2H; 1.80 (7.5), quint, 2H; 1.49-1.43, m, 2H; 1.41-1.36, m,
2H; 1.34-1.31, m, 4H; 0.91 (7.0), t, 3H. (E)-5b: 7.92 (8.0, 1.5),
dd, 2H; 7.67 (7.8, 1.3), dd, 2H; 7.55 (7.6, 1.2), td, 2H; 7.49, m,
2H overlapped with (Z)-5b; 3.96, s, 1H; 2.47 (8.0), t, 2H
overlapped with (Z)-5b; 0.80 (7.0), t, 3H; other multiplets were
poorly defined. (Z)-6b: 3.90, s, 1H; 2.43 (7.8), t, 2H; 1.73 (7.5),
quint, 2H; 1.41-137, m, 2H; 1.34-1.19, m, 8H; 0.83 (6.8), t,
3H. (E)-6b: 7.85 (8.0, 1.0), dd, 2H; 7.60 (7.5, 1.0), dd, 2H; 7.48
(
7.0), quint, 2H; 1.23, m, 4H; 0.83 (6.8), t, 3H. C: 30.8 (CH
2
),
2 2 2 3
6.4, (CH ), 21.8 (CH ), 20.0 (CH ), 13.7 (CH ). 4a. H: 2.37
1
2
(
7.3), t, 2H; 1.50 (7.3), quint, 2H; 1.21, m, 6H; 0.83 (7.0), t,
1
3
3
H. C: 30.8 (CH
), 13.9 (CH ). 5a. H: 2.36 (7.0), t, 2H; 1.50 (7.3), quint,
H; 1.21, m, 8H; 0.85 (7.0), t, 3H. C: 31.4 (CH
8.3 (CH ), 26.7 (CH ), 22.4 (CH ), 20.0 (CH ), 14.0 (CH
2 2 2 2
), 28.3 (CH ), 26.6 (CH ), 22.2 (CH ), 20.0
1
(
CH
2
3
1
3
2
2
), 28.6 (CH
2
),
2
2
2
2
2
3
). 6a.
1
H: 2.36 (7.3), t, 2H; 1.50 (7.3), quint, 2H; 1.94-1.25, m, 10 H;
.87 (7.3), t, 3H. 13C: 31.6 (CH
), 28.9 (CH ), 28.7 (CH ), 28.6
CH ), 26.7 (CH ), 22.5 (CH ), 20.0 (CH ), 14.0 (CH ). 8a. H:
.37 (7.3), t, 2H; 1.48 (7.5), quint, 2H; 1.25, (7.7), sext, 2H;
0
(
2
2
2
1
2
2
2
2
3
2
0
1
3
.82 (7.5), t, 3H. C: 28.6 (CH
2
), 21.8 (CH
2 2
), 19.8 (CH ), 13.2
1
(
CH
3
). 9a. H: 2.36 (7.3), t, 2H; 1.49 (7.3), quint, 2H; 1.20, m,
1
3
4
H; 0.81 (6.8), t, 3H. C: 30.7 (CH
2
), 26.3 (CH
2 2
), 21.7 (CH ),
1
2
0.0 (CH ), 13.7 (CH ). 10a. H: 2.36 (7.3), t, 2H; 1.48 (7.0),
2 3
1
3
quint, 2H; 1.19, m, 6H; 0.82 (6.8), t, 3H. C: 30.8 (CH
CH ), 26.6 (CH ), 22.2 (CH ), 20.0 (CH ), 13.8 (CH ). 11a. H:
.36 (7.3), t, 2H; 1.49 (7.1), quint, 2H; 1.22, m, 8H; 0.85 (7.0),
2
), 28.2
1
(
2
2
2
2
3
2
13
2 2 2 2
t, 3H. C: 31.4 (CH ), 28.6, (CH ), 28.3 (CH ), 26.6 (CH ), 22.4
J. Org. Chem, Vol. 70, No. 24, 2005 9769

Rangappa et al.
(
7.5, 1.2), td, 2H; 7.42, m, 2H overlapped with (Z)-6b; 3.89, s,
H; 2.40 (7.5), t, 2H; 0.75 (7.3), t, 3H; other peaks were poorly
defined.
2H; 2.42 (7.5), t, 2H; 1.43 (7.5), quint, 2H; 1.20 (7.5), sext, 2H;
1
3
1
0.82 (7.5), t, 3H. C: 207.7 (-CdO), 137.7 (quat), 135.5 (CH),
135.4 (CH), 131.2 (CH), 130.5 (CH), 118.0 (quat), 52.0 (CH
2
),
Mass Spectroscopy of Ylides. 2b: 315 (M + 1; 100), 229
41.5 (CH ), 25.7 (CH ), 22.5 (CH , 13.9 (CH ).
2
2
2
3
(
M - 113; 5), 216 (M - 98; 60), 184 (M - 130; 10). 4b: 343 (M
Preparation of 5-[(2-Keto)-3-pentyl]thianthrenium Tet-
•
+
-
+
1; 30), 325 (M - 17; 90); 229 (M - 113; 45), 216 (M - 126;
rafluroborate (13). A solution of Th BF in 10 mL of MeCN
4
1
00), 183 (M - 159; 35).
was prepared in situ from 250 mg (1.16 mmol) of Th and 150
mg (1.28 mmol) of NOBF . To the stirred solution was added
Elemental Analyses. 2b. Calcd for C18
H
18
S
2
O: C, 68.7; H,
4
5
.76; S, 20.4 Found: C, 68.3, H, 5.47, S, 20.2.
Reactions of 1-(5-Thianthreniumyl)alkynes on Alu-
150 mg (1.74 mmol) of 2-pentanone. The blue color of the
solution faded to pale yellow during 1 h. Ether was added,
causing the precipitation of 165 mg (0.42 mmol, 36%) of 13.
mina. A. Isolation of 6c from 6a. A solution of 200 mg (0.454
mmol) of 6a in 20 mL of chloroform was stirred with 4 g of
alumina for 3 h. After filtration and washing the alumina with
chloroform the combined chloroform solutions was reduced to
small volume and loaded onto a silica gel column. Th was
eluted with hexane. Continued elution with hexane/ethyl
acetate 9/1 gave a small amount of product containing some
Th. Preparative TLC on silica gel plates gave 4.5 mg of yellow
1
H NMR, CDCl , δ (J): 8.16 (7.8, 1.3), dd 1H; 8.09 (8.0, 1.0),
3
dd, 1H; 7.97 (8.3, 1.3), dd, 1H; 7.90 (7.8, 1.3), dd,1H; 7.85 (7.3,
1.0), td, 1H; 7.76 (7.7, 1.3), td, 1H; 7.71 (7.7, 1.2), td, 1H; 7.67
(7.8, 1.3), td, 1H; 5.673 (5.0) and 5.665 (5.0), overlapping d,
1H; 2.23-2.16, m, 1H; 2.15, s, 3H; 1.43-1.39, m, 1H; 0.94 (7.5),
1
3
t, 3H. C: 203.5 (-CdO), 138.5 (quat), 137.6 (quat), 136.5
(CH), 136.0 (CH), 135.8 (CH), 135.3 (CH), 131.6 (CH), 131.4
(CH), 130.9 (CH), 130.4 (CH), 118.3 (quat), 115.8 (quat), 67.4
CH), 28.5 (CH ), 21.6 (CH ), 9.0 (CH ).
oil, shown with NMR spectroscopy to be 1-hydroxy-2-decanone
1
(
6c). H NMR, δ (J): 4.23 (3.0), d, 2H; 3.11, b s, (OH), 2.41
2
2
3
(
7.5), t, 2H; 1.63 (7.5), quint, 2H; 1.29-1.26, m, 10H; 0.88 (7.0),
Conversion of 13 into 3-Hydroxy-2-pentanone (14). A
1
3
t, 3H. C: 209.9 (CdO), 68.1 (-CH
3
2
2
OH), 38.4 (-CH
), 29.06 (CH ), 23.7 (CH
3
). 6c was prepared by oxidation of 1,2-
2
CdO),
solution of 30 mg (0.077 mmol) of 13 in 2 mL of CDCl
3
1.8 (CH
2.6 (CH
2
), 29.23 (CH
), 14.1 (CH
2
), 29.19 (CH
2
2
2
),
containing 5 µL of added water was stirred with 600 mg of
alumina for 3 h. NMR spectroscopy showed that Th had been
formed. The remaining signals were deduced to be those of
2
1
1
1
13
decanediol and had H and C NMR spectra agreeing with
the spectra of isolated 6c.
1
4. Water was added deliberately in this control experiment,
B. Identification of 1c and 4c. Attempts to isolate 1c and
c were unsuccessful. Each was identified by NMR spectros-
rather than relying on adventicious water in solvent, to ensure
4
1
complete and quicker reaction. H NMR, δ (J): 4.18 (6.5, 4.4),
copy in a mixture with the corresponding ylide, however. Thus,
dt, 1H; 3.47 (5.0), d, (OH); 2.20, s, 3H; 1.96-1.88, m, 1H; 1.68-
as described in the isolation of 4b, part of the residue obtained
13
1.60, m, 1H; 0.95 (7.5), t, 3H. C: 209.9 (-CdO), 77.6 (CH),
26.5 (CH
3
from concentrating the MeCN solution was dissolved in CDCl .
2 3 3
), 25.2 (CH ), 8.2 (CH ).
The NMR spectrum showed the dominant presence of 4b and
1
smaller peaks assignable to 4c. In the H spectrum these peaks
Acknowledgment. H.J.S. thanks the Welch Foun-
were at 4.2 ppm (-CH OH) and 0.86 (J ) 6.8) ppm (CH ). The
2
3
1
13
dation for support (Grant D-0028). K.H.W. thanks the
Welch Foundation for support (Grant C-0976) and the
purchase of the CCD and the National Science Founda-
tion for support (Grant CHE-9983352). We thank Mr.
David W. Purkiss (TTU) for the 500-MHz NMR spec-
troscopy.
remaining H signals were merged with those of 4b. C: 68.0,
8.4, 31.4, 28.9, 23.5, 22.3,13.9. The assigned signals were in
agreement with those of 4c prepared by oxidation of 1,2-
3
1
2
1
13
octanediol. Similar treatment of 1a gave H and C NMR
1
13
evidence for the presence of 1c. H: 4.21; 0.93 (7.3). C: 68.1,
1
3
4
0.1, 17.0, and 13.7. The C data agreed with those reported
1
13
by Matsumoto et al.; H NMR data were not reported.
Conversion of 2b into 2d. To a solution of 10.5 mg (0.033
mmol) of 2b in 2 mL of chloroform was added 4 µg (0.029
Supporting Information Available: X-ray crystallo-
graphic information data for compounds 1, 4, and 6a in CIF
format and ORTEP diagram (Figure S1) for 1. This material
is available free of charge via the Internet at http://pubs.acs.org.
4
mmol) of HBF . A white precipitate formed and was recovered,
giving 8.5 mg (0.027 mmol, 82%) of 2d, mp 178-180 °C (dec).
1
H NMR, CDCl
3
, δ (J): 8.15 (8.0, 1.0), dd, 2H; 7.92 (8.0, 1.0),
dd, 2H; 7.79 (7.5, 1.5), td, 2H; 7.68 (7.6, 1.3), td, 2H; 4.84, s,
JO051317Q
9770 J. Org. Chem., Vol. 70, No. 24, 2005