Fine-tuning latent fingerprint detection on paper using 1,2-indanedione bi-functional reagents

Article abstract of DOI:10.1016/j.tet.2015.07.072

In order to address the need for consistency and generality in chemical methods developed for detection of latent fingerprints on paper substrates, a practical protocol was developed using 1,2-indanedione-based bi-functional reagents. A series of novel bi

Full text of DOI:10.1016/j.tet.2015.07.072

Tetrahedron 71 (2015) 7620e7629
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Fine-tuning latent fingerprint detection on paper using
1,2-indanedione bi-functional reagents
*
ꢀ
Jisun Lee, Madeleine M. Joullie
Department of Chemistry, University of Pennsylvania, 231 S. 34th Street, Philadelphia, PA 19104-6323, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 13 May 2015
Received in revised form 27 July 2015
Accepted 28 July 2015
Available online 1 August 2015
In order to address the need for consistency and generality in chemical methods developed for detection
of latent fingerprints on paper substrates, a practical protocol was developed using 1,2-indanedione-
based bi-functional reagents. A series of novel bi-functional reagents were designed and synthesized
using a concise, five-step sequence. An optimized development condition that is tailored to the type of
paper substrate that requires processing was discovered, allowing potential application in practical
criminal work where evidence processing is an irreversible process. The study also provided an insight to
the underlying mechanism of interaction between the bi-functional reagent and fingerprint residue.
Ó 2015 Elsevier Ltd. All rights reserved.
Keywords:
Forensic science
Fingerprint detection
1,2-Indanedione
Multi-metal deposition
1. Introduction
As a result, even the most sensitive chemical reagents do not always
produce a sufficiently clear image.
Latent (hidden or invisible) fingerprint detection on paper
substrates is a crucial component in criminal investigations, and is
used widely in forensic science due to the fact that society relies
heavily on such cellulosic materials (official documents, currency
printing, packaging, etc.).1 When a fingerprint is deposited on
a paper substrate, amino acids present in natural skin secretions
bind to the cellulose of the paper preserving either a visible or la-
tent impression of the friction ridge patterns. Latent fingerprints
are the most common, yet problematic type of evidence found at
crime scenes, since they require special methods for development
and visualization. Over the years, significant amount of research
has been devoted to the discovery and development of chemical
methods based on the detection of amino acids present in natural
skin secretions.1 Although a wide variety of chemical reagents
(ninhydrin, 1,2-indanedione, 1,8-diazafluoren-9-one) have been
identified from this collective effort,1,2 over 50% of all fingerprints3
still escape detection. Existing chemical methods rely on a stoi-
chiometric reaction between the detection reagent and an amino
acid, thus setting an upper limit to sensitivity. Furthermore, latent
fingerprints often do not contain adequate quantities of amino
acids, and their composition may vary depending on numerous
factors, such as an individual’s general health, diet, gender and age.1
To remedy this limitation, attention has been directed toward
utilizing nanotechnology in the development process.1b,3,4 In par-
ticular, the versatility of surface modification of nanoparticles has
been exploited, allowing precise targeting of various components
present in fingerprint residues.3,4 In terms of increasing sensitivity,
a process that employs metastable silver colloid solution, silver
physical developer (Ag-PD),1b,5 has been used as a post-treatment
enhancement of gold nanoparticle (AuNP) treated fingerprint de-
posits on paper substrates, which is a form of multi-metal de-
position (MMD).1b,1d,6 Another common development method is
single-metal deposition (SMD),1b,1d,7 in which the enhancement of
AuNP treated fingerprint residues occurs via reinforcement with
gold colloids in aqueous solution rather than with silver. Although
development techniques that employ nanotechnology have been
rapidly evolving, sensitivity still remains a tough challenge. For
example, current developed processes display inconsistent results
amongst various protocols, even for the same type of nano-
particles.3 The precise underlying mechanisms involved in the in-
teraction between the AuNPs (or any other nanoparticles) and the
fingerprint residue is yet to be elucidated, most likely due to the
complex composition of the fingerprint residue.8 Thus far, the
mechanism was broadly assumed to be a simple ionic interaction
between the negatively charged citrate stabilized AuNPs and the
positively charged amino acids of the fingerprint residue at low
pH.3,5e8 The surprising lack of mechanistic study in this field was
brought to attention only recently.8 Understanding the precise
chemical interaction required for latent fingerprint detection on
* Corresponding author. Tel.: þ1 215 898 3158; fax: þ1 215 573 9711; e-mail
ꢀ
address: mjoullie@sas.upenn.edu (M.M. Joullie).
http://dx.doi.org/10.1016/j.tet.2015.07.072
0040-4020/Ó 2015 Elsevier Ltd. All rights reserved.

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J. Lee, M.M. Joullie / Tetrahedron 71 (2015) 7620e7629
7621
paper substrates is essential in developing protocols that will allow
consistent results to be obtained. Moreover, in terms of practical
criminal investigation, it is important to be able to choose the op-
timal development conditions amongst the numerous methods
that are in existence, since once the evidence is chemically pro-
cessed, it cannot be reprocessed.
available 5-chloro-1-indanone was treated with the requisite po-
tassium alkyltrifluoroborate salt using the SuzukieMiyaura cross-
coupling reaction to afford the corresponding chain coupled
product 7e12 in acceptable yields. In line with our previous find-
ings,11
2-dicyclohexylphosphino-20,60-diisopropoxybiphenyl
(RuPhos) was the ligand of choice for all the substrates. Slight
variability in yields was observed for the cross-coupling reaction,
possibly due to the different side chain lengths. In general, longer
side chains afforded modest yields in comparison to shorter ones.
Subsequent displacement of the tosylate moiety with potassium
thioacetate generated intermediates 13e18 in good yields. Forma-
tion of the oxime (19e24), followed by conversion to the desired
1,2-indanedione analogues 25e30 was accomplished using a vari-
ation of previously developed methods2eef,9 in quantitative yields
without requiring the use of silica gel chromatography purification
steps. Not surprisingly, in some cases, a negligible amount of the
thiol 1,2-indanedione derivative was observed under the acidic
aqueous conditions employed in the last step. The mixture of major
and minor 1,2-indanedione products was carried onto the next step
of AuNP functionalization, since in situ removal of the thiol pro-
tecting group occurs naturally during ligand exchange.3,12
We have been investigating the mechanism9 and application of
various 1,2-indanedione analogues in detection of latent fingerprints
since our first discovery of the chemical reagent in 1997.2eef Because
of its highly fluorescent properties upon interaction with fingerprint
residue, 1,2-indanedione rapidly became a standard reagent in fo-
rensic laboratories around the world.1b However, due to limitations
set by the stoichiometric nature of the reaction, the variability in the
amino acid (or sweat) content on a given fingerprint residue, and the
need of using specialized equipment (such as lasers) for visualization,
the focus of our recent research efforts has been shifted to application
of the well-established 1,2-indanedione interactionwith amino acids
in fingerprint residues2,10 as a platform to utilize nanotechnology as
a promising alternative. We have recently reported the viability of
using a bi-functional reagent containing a 1,2-indanedione motif,
that is, appended bya ten-carbon alkylthiol chain, following the basic
principle of MMD (Scheme 1).11 In order to address the challenging
issue of achieving consistency in the development of latent finger-
prints as well as elucidating the underlying mechanism between the
functionalized AuNPs and fingerprint residues, a thorough in-
vestigation of the novel method was deemed crucial. Herein, we wish
to report a practical, generalized protocol of using 1,2-indanedione
functionalized AuNPs for detection of latent fingerprints on various
types of paper substrates and an insight to the mechanism of the
interaction.
Scheme 2. Synthesis of 1,2-indanedione derivatives 25e30. *Synthesis of 13 was
achieved using a Mitsunobu reaction (see experimental details).
Scheme 1. Latent fingerprint development using 1,2-indanedione based bi-functional
reagent.
2.2. Synthesis of bi-functional reagents
Finally, AuNPs stabilized by dodecyldimethylammonium bro-
mide (DDAB) was synthesized following a modification of a known
procedure,13 and subsequently functionalized via ligand exchange
with 1,2-indanedione analogues 19e24 to afford the corresponding
bi-functional reagents. UVevis spectroscopy and TEM were used to
determine both relative particle size and degree of aggregation of
functionalized AuNPs.14 UVevis spectra showed clear shifts in gold
plasmon band after ligand exchange with respect to the as-
prepared DDAB capped AuNP colloids, indicating changes in the
AuNP environment (Fig. 1a). The relative extent of peak broadening
and red/blue shift in gold plasmon band that were observed from
changes in chain length of bi-functional reagents were reasonable
considering the corresponding interparticle separation of AuNPs
(Fig. 1a). Generally, with shorter ligand chain lengths, separation
between particles become smaller (exhibited as aggregation or
even fusion), which increases the electromagnetic coupling be-
tween the particles and results in larger shifts.13,15 For example, the
relative degree of aggregation appeared to be more pronounced for
2. Results and discussion
Although the modified MMD protocol using a ten-carbon chain
bi-functional reagent produced acceptable fingerprint images on
paper substrates, the contrast was often poor and inconsistent re-
sults were obtained when using sebum-rich (lipids and other hy-
drophobic substances naturally present in skin) fingerprint
deposits. Therefore, an assortment of 1,2-indanedione-based bi-
functional reagents that varied in chain lengths was generated to
study the resulting chemical effects during the interaction between
the reagent and the fingerprint residue, which would ultimately
allow the development of a generalized procedure.
2.1. Synthesis of 1,2-indanedione analogues
The synthesis of 1,2-indanedione analogues was achieved using
a
concise, four-step procedure (Scheme 2).11 Commercially

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J. Lee, M.M. Joullie / Tetrahedron 71 (2015) 7620e7629
7622
three-, five-, and eight-carbon bi-functional derivatives over others,
which was implied by either increase in peak broadening or ap-
pearance of second absorbance around>700 nm (Fig. 1a). TEM
images of the bi-functional reagents also showed relative degrees
of aggregation, where the most pronounced difference was ob-
served between eight-carbon derivative and twelve-carbon de-
rivative (Fig. 1b,c).
Fig. 2. Model system for determining bi-functional reagent efficiency in detecting
amino acids on paper substrate. Visible images obtained from L-leucine (0.0075 M in
30% dioxane in water mixture) treated stamp stamped on a WhatmanÒ filter paper,
which was cut in half, where each half was treated with different bi-functional reagent
chain derivative (0.01% w/v in dimethyl sulfoxide) followed by water rinse then post-
enhancement with Ag-PD. The bi-functional reagent indicating carbon chain length
used is shown under each half image. The bottom right image where the right half was
treated with Ag-PD only was used as the control.
In all cases, a positive mark was obtained, in which the silver
deposition was more apparent on the mark in comparison to the
background. This result strongly suggests the preferential in-
teraction of the bi-functional reagent with the amino acid regard-
less of chain length. Furthermore, of the bi-functional reagents
tested, the eight-carbon chain derivative produced the most pro-
nounced image after processing, while the ten-carbon chain de-
rivative afforded better contrast against the background. Taken
together, these results suggest that there is an optimal chain length
for the detection of amino acids on paper.
With this promising result in hand, we then tested the bi-
functional reagents on various types of paper substrates bearing
fingerprint deposits. Thickness of paper gave a remarkable differ-
ence in reactivity and subsequently observed contrast (Fig. 3). For
instance, consistent with observations on the model system, for
Fig. 1. a) UVevis absorption spectrum comparing various bi-functional reagents syn-
thesized (notation on spectrum indicates carbon chain length). As-is AuNP is the as-
prepared DDAB stabilized AuNPs. As-is AuNP lmax¼567 nm, 3cAuNP lmax¼555 nm,
5cAuNP lmax¼557 nm, 8cAuNP lmax¼576 nm, 10cAuNP lmax¼557 nm, 12cAuNP
lmax¼557 nm, 14cAuNP lmax¼542 nm. All measurements taken in dimethyl sulfoxide.
b) TEM image of 8cAuNP. c) TEM image of 12cAuNP.
thicker WhatmanÒ filter paper substrates (180e190
mm in thick-
ness), the ten-carbon chain derivative gave the best results in terms
of contrast (Fig. 3a), with the twelve-carbon chain giving almost
similar results (Fig. 3b). Eight-carbon chain derivative however,
resulted in poor contrast, although the rate of silver deposition
during Ag-PD treatment seemed the fastest and in greatest quan-
2.3. Application of bi-functional reagents
Application of these reagents in the development of latent fin-
gerprints on paper was examined next following the initially de-
veloped conditions.11 In order to determine and compare the
relative efficiency of the bi-functional reagents in detecting amino
acids, a controlled amino acid substrate system was designed as
a model system. A stamp with an intricate snowflake engraved
tity. However, with much thinner copy paper substrates (100 mm in
thickness), the five-carbon chain derivative afforded the best image
(Fig. 3c), and the eight-carbon chain derivative following was
a close second (Fig. 3d). Optimal post-treatment enhancement
conditions were also identified depending on the thickness of the
paper substrate. Ag-PD worked well for thicker WhatmanÒ filter
paper substrates (Fig. 3aeb), while SMD worked better for thinner
copy paper substrates (Fig. 3ced). For thinner paper, Ag-PD gave
rise to images with poor contrast, while for thicker paper sub-
strates, SMD offered almost no image enhancement, but rather, the
difference was significantly augmented by Ag-PD.
A correlation between the relative aggregation of the bi-
functional reagent and the thickness of the paper could explain
the obtained results. For thicker paper substrates, relatively less
aggregated AuNPs (ten- and twelve-carbon derivatives) produced
good image contrast, while for thinner paper, more aggregated
particles (five- and eight-carbon derivatives) worked better. How-
ever, there is a window of optimal chain lengths for different type of
paper substrates. For example, the shortest, and thus most aggre-
gated three-carbon chain derivative displayed poor image contrast,
design was coated with a diluted solution of L-leucine and sub-
sequently stamped gently on a WhatmanÒ filter paper (Fig. 2). To
eliminate the possibility of obtaining misleading results,8 the
stamped paper substrate (print invisible to the naked eye) was left
to age for at least 2 days and then processed by immersing the
paper in a solution of the requisite bi-functional reagent for 1 min.
Subsequent water rinse followed by post-treatment with standard
Ag-PD solution for <10 s gave rise to visible marks (Fig. 2). Since
AuNPs that are functionalized with polar ligands (such as ligands
containing a carboxylic acid16 or an acyl moiety3) have been shown
to readily bind to cellulose of the paper via hydrogen-bonding in-
teractions, it was crucial to obtain selective preferential binding
with the fingerprint residue over the interaction with cellulose in
order to achieve good image contrast after development.

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J. Lee, M.M. Joullie / Tetrahedron 71 (2015) 7620e7629
7623
using the twelve-carbon reagent (Fig. 4c). No significant difference
in the obtained fingerprint image was apparent, thus suggesting
that the acidity may not necessarily play a role in the current
system. Finally, latent fingerprints that were unintentionally
charged and aged over a one month period were detected on
paper used for official documents (100% cotton paper, 150 mm in
thickness) using the twelve-carbon chain derivative, following the
developed protocol for thicker paper substrates (Fig. 4d), further
supporting the efficiency and practicality of the bi-functional
reagents.17
Fig. 3. Latent fingerprints on different types of paper developed using various bi-
functional reagents (0.01% w/v in dimethyl sulfoxide) followed by water rinse and
subsequent enhancement with Ag-PD or SMD. a) WhatmanÒ filter paper, treated with
the ten-carbon chain bi-functional reagent followed by Ag-PD. b) WhatmanÒ filter
paper, treated with the twelve-carbon chain derivative, followed by Ag-PD. c) Standard
copy paper, treated with the five-carbon chain derivative followed by SMD. d) Standard
copy paper, treated with the eight-carbon chain derivative with no enhancement (no
SMD or Ag-PD).
suggesting significantly decreased specificity for both thick and
thin paper substrates. The longest, thus relatively less aggregated
fourteen-carbon chain derivative gave rise to weak prints on
thicker paper substrates, and almost no visible prints for thinner
paper. Interestingly, in some cases, for thinner paper substrates, the
reaction between the five- or eight-carbon chain derivatives and
fingerprint deposits was so rapid and facile that visible prints with
good contrast appeared without the need for the second en-
hancement step (Fig. 3d).
Fig. 4. Latent fingerprints developed using the twelve-carbon chain derivative
(0.01% w/v in dimethyl sulfoxide) followed by water rinse, then Ag-PD. a) On What-
manÒ filter paper, left half processed with twelve-carbon derivative for 2 min then Ag-
PD <5 s, right half with Ag-PD only 2 min. b) On WhatmanÒ filter paper, left half
processed with twelve-carbon derivative for 2 min then Ag-PD <5 s, right half with
citrate-capped AuNPs (avg. diameter 60 nm, same concentration) for 2 min then Ag-
PD<5 s c) On WhatmanÒ filter paper, left half processed with twelve-carbon derivative
for 2 min then Ag-PD <5 s, right half paper pretreated with 2.5% w/v malic acid in
water for 10 min then processed with twelve-carbon derivative for 2 min then Ag-PD
<5 s d) On 100% cotton paper used for official documents (a.k.a. resume paper), >1
month old fingerprint, processed with the twelve-carbon chain derivative for 3 min,
then Ag-PD <5 s.
In terms of mechanism of binding, the well-established re-
action between 1,2-indanedione and amino acids2,10 appeared to
be the main reaction pathway. For example, reliable and consistent
results that were in good agreement with the present findings
were obtained with eccrine-rich fingerprints, while inconsistent
results were obtained using sebum-rich fingerprints. In order to
prove the efficacy of the bi-functional reagents in detecting latent
fingerprints, a split-print comparison1,2 was conducted (Fig. 4). For
the split-print comparison, a fingertip was intentionally charged
with eccrine secretions (e.g., saliva), and evenly distributed on the
surface. The fingertip was then stamped onto a paper substrate
and aged for at least 2 days. The paper was then cut in half and
processed using different conditions keeping concentration and
reaction time consistent. The optimized protocol for thicker filter
paper using the twelve-carbon derivative performed significantly
better in all cases when compared side by side with other known
conditions. For instance, at the optimized reaction time, Ag-PD
alone did not afford clear fingerprints (Fig. 4a). When AuNPs
that lack 1,2-indanedione moiety were used, relatively weak prints
lacking in detail were observed, which could be attributed to the
normal electrostatic interaction1,8 between the AuNP and amino
acid component of the fingerprint residue (Fig. 4b). There have
been reports on the importance of acidity (wpH 3) with regards to
obtaining quality prints.8,18 To test this hypothesis in the current
system, one half of the filter paper that has eccrine-rich finger-
print deposit was pretreated with a 2.5 w/v% malic acid aqueous
solution (pH¼2.29 at 21.7 ꢀC) for 10 min, air-dried, and processed
3. Conclusions
In summary, a practical, generalized protocol was developed for
latent fingerprint detection on paper substrates using 1,2-
indanedione-based bi-functional reagents. A series of novel bi-
functional reagents were designed and successfully synthesized
using a concise, five-step protocol in the process. The present op-
timized protocol displayed efficiency and gave consistent results.
When compared to existing chemical detection methods, the de-
velopment process was very fast, where clearly visible prints with
good image contrast was obtained in less than 20 min. The de-
veloped latent fingerprints that were obtained were of sufficient
quality to be recorded using a standard iPhone camera (iPhone 5S),
eliminating the use of specialized equipment. Furthermore, results
obtained from this study gave insight to the underlying mechanism
of the interaction between the bi-functional reagent and finger-
print residue. Overall, the study provided a generalized de-
velopment condition tailored to the type of paper substrate that
requires processing for latent fingerprints, allowing potential ap-
plication in cases where sensitive detection reagents are needed.

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J. Lee, M.M. Joullie / Tetrahedron 71 (2015) 7620e7629
7624
4. Experimental section
a glove box. The flask was then removed and to it was added a so-
lution of the tosylate (1.19 g, 4.95 mmol) in anhydrous CH2Cl2 (17 mL)
via cannula addition. The resulting mixture was brought to 0 ꢀC,
followed by dropwise addition of pinacolborane (1.07 mL,
7.43 mmol). The reaction mixture was left to stir and allowed to
warm to room temperature overnight. The reactionwas quenched by
water (5 mL), stirred for 5 min, and the resulting mixture was sep-
arated. The aqueous layer was extracted with diethyl ether (15 mL,
three times). The combined organic layers were dried over MgSO4,
filtered, and concentrated. Purification by silica gel chromatography
(20% EtOAc/Hexanes) afforded 5-(4,4,5,5-Tetramethyl-1,3,2-
dioxaborolan-2-yl)pentyl 4-methylbenzenesulfonate (36) as an
oil (1.64 g, 90%). Rf 0.5 (20% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
All reactions were performed under an argon atmosphere ex-
cept where otherwise noted. Solvents were purchased from Fisher
Scientific and dried via an alumina column. Anhydrous toluene in
Acroseal bottle was used without further purification prior to use.
Milli-Q (18 MU) water (Millipore; Billerica, MA, USA) was used for
the synthesis of gold nanoparticles. Flash chromatography was
carried out on Merck silica gel 60 (240e400 mesh) using the sol-
vent conditions listed under individual experiments. Analytical
thin-layer chromatography was performed on Merck silica gel
(60F-254) plates (0.25 mm). Visualization of thin-layer chroma-
tography plates was effected with ultraviolet light or phosphomo-
lybdic acid (PMA) stain. Melting points (ꢀC) are uncorrected. Proton
magnetic resonance spectra (1H NMR), Carbon magnetic resonance
spectra (13C NMR), Fluorine magnetic resonance spectra (19F NMR),
and Boron magnetic spectra (11B NMR) were performed on a Bruker
d
7.80 (d, J¼8.3 Hz, 2H), 7.35 (dd, J¼8.6, 0.6 Hz, 2H), 4.03 (t, J¼6.6 Hz,
2H), 2.46 (s, 3H), 1.64 (dq, J¼13.9, 6.7 Hz, 2H), 1.40e1.29 (m, 4H), 1.24
(s, 12H), 0.74 (t, J¼7.6 Hz, 2H); 13C NMR: (125 MHz, CDCl3)
d 144.6,
133.3, 129.8, 127.9, 83.0, 70.7, 28.6, 27.9, 24.8, 23.4, 21.6; 11B NMR
NMR operating at 500, 125, 470, and 128 MHz, respectively. All 11
B
(128.4 MHz, CDCl3) d
33.08; IR (cmꢁ1): 2978, 2933, 2864, 1598, 1462,
chemical shifts were referenced to external BF3$OEt2 (0.0 ppm)
with a negative sign indicating an upfield shift. Infrared spectra (IR)
were obtained on a PerkineElmer 281-B spectrometer or a Bruker
A-P spectrometer. High resolution mass spectra (HRMS) were ob-
tained on a Micromass Autospec or a Waters LCTOF-Xe premier.
Ultraviolet absorption spectroscopy (UVevis) was performed on
a JASCO V-650 spectrophotometer (JASCO Analytical Instruments;
Easton, MD, USA) equipped with a JASCO PC-734R multichannel
Peltier using quartz cells with 1 cm path lengths. Transmission
electron microscopy (TEM) was performed using a JEOL 1400 mi-
croscope operating at 120 keV. Scanning electron microscopy
(SEM) was performed on a JEOL 7500F HRSEM operating at 5.0 kV.
All other starting materials and reagents were purchased from
SigmaeAldrich, TCI, Acros, or Strem and were used without further
purification unless specified. Silver physical developer (Ag-PD)
solution was purchased from Arrowhead Scientific Inc. Fingerprint
images were taken with a standard iPhone 5S camera.
1362, 1321, 1188, 1177, 1145, 1098, 967, 937, 844, 815, 664, 577, 555;
HRMS (ESI) m/z calculated for C18H29BO5S (MþNa)þ: 391.1730,
found: 391.1726.
To a stirred solution of 36 in acetonitrile (5 mL) was added
aqueous potassium bifluoride, 4.5 M KHF2 (aq) (4.5 mL). The
resulting mixture was stirred at room temperature for 1 h. The
solution was concentrated, and left under reduced pressure over-
night. Hot acetonitrile (50 mL) was added to the solid and the so-
lution was filtered by hot gravity filtration (or alternatively, Soxhlet
extraction). The filtrate was evaporated, re-dissolved in small
amount of cold diethyl ether (5 mL) and filtered to afford the de-
sired potassium alkyl trifluoroborate salt (2) in 96% yield: White
solid. mp 158 ꢀC. 1H NMR: (500 MHz, acetone-d6)
d 7.77 (d,
J¼8.2 Hz, 2H), 7.48 (d, J¼7.9 Hz, 2H), 3.96 (t, J¼6.6 Hz, 2H), 2.42 (s,
3H), 1.53e1.46 (m, 2H), 1.16e1.09 (m, 4H), 1.08e1.02 (m, 2H); 13C
NMR: (125 MHz, acetone-d6) d 145.2, 133.1, 130.6, 127.9, 71.9, 29.03,
28.92, 25.49, 25.48, 21.6; 11B NMR (128.4 MHz, acetone-d6)
d 5.24;
19F NMR (470.8 MHz, acetone-d6)
d
ꢁ136.79; IR (cmꢁ1): 2920, 2856,
Synthesis of potassium alkyltrifluoroborate side chains
1599, 1354, 1332, 1308, 1293, 1273, 1251, 1190, 1174, 1095, 1069,
1020, 944, 914, 883, 838, 809, 779, 723, 705, 689, 665, 567, 552;
HRMS (ESI) m/z calculated for C12H17BO3F3S (MꢁKþ)þ: 309.0937,
found: 309.0944.
4.3. Potassium trifluoro(8-(tosyloxy)octyl)borate (3)
4.1. Potassium trifluoro(3-hydroxypropyl)borate (1)
General procedure A was followed using the known corre-
sponding tosylate (oct-7-en-1-yl 4-methylbenzenesulfonate)20 in
the first step and 8-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)
octyl 4-methylbenzenesulfonate (37) in the second step: Colour-
Synthesized following known literature method.19 White solid.
mp 175 ꢀC. 1H NMR spectra obtained was in good agreement with
the reported spectra.19 1H NMR: (500 MHz, DMSO-d6)
d
3.90 (t,
less oil. Rf 0.65 (20% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d 7.79
J¼5.4 Hz, 1H), 3.24 (td, J¼7.4, 5.6 Hz, 2H), 1.32e1.26 (m, 2H), ꢁ0.13
(d, J¼8.31 Hz, 2H), 7.35 (d, J¼8.51 Hz, 2H), 4.04e4.00 (m, 2H), 2.45
to 0.18 (m, 2H).
(s, 3H), 1.69e1.59 (m, 4H), 1.39e1.22 (m, 20H), 0.75 (t, J¼7.82 Hz,
2H); 13C NMR: (125 MHz, CDCl3)
d 144.5, 133.1, 129.7, 127.8, 82.8,
4.2. Potassium trifluoro(5-(tosyloxy)pentyl)borate (2)
70.6, 32.1, 31.6, 29.0, 28.9, 28.8, 28.7, 25.2, 24.7, 23.8, 22.5, 21.5, 14.0;
11B NMR (128.4 MHz, CDCl3) 33.68; IR (cmꢁ1): 2977, 2928, 2857,
d
4.2.1. General procedure A. To a stirred solution of 4-penten-1-ol
(0.6 mL, 5.81 mmol) in anhydrous CH2Cl2 (11 mL) was added trie-
thylamine (1.21 mL, 8.71 mmol) followed by DMAP (28 mg,
0.232 mmol) and TsCl (1.1 g, 5.81 mmol). The resulting mixture was
stirred at room temperature overnight. The reaction was diluted
with water (10 mL) and extracted with chloroform (10 mL, three
times). The combined organic layers were washed with aqueous
satd NH4Cl (10 mL), separated, dried over MgSO4, filtered, and
concentrated. Silica gel column chromatography purification (20%
EtOAc/Hexanes) afforded the corresponding known tosylate20 (31)
as an oil (1.19 g, 86%).
1598,1495, 1466,1363,1320,1272,1213,1188,1177,1145,1098,1019,
966, 936, 845, 815, 664, 577, 555; HRMS (ESI) m/z calculated for
C
21H35BO5S (MþH)þ: 411.2377, found: 411.2372. The desired po-
tassium alkyl trifluoroborate salt (3) was obtained in 77% yield:
White solid. mp>200 ꢀC. 1H NMR: (500 MHz, acetone-d6)
d 7.81 (d,
J¼8.18 Hz, 2H), 7.50 (d, J¼8.29 Hz, 2H), 4.05 (t, J¼6.41 Hz, 2H), 2.47
(s, 3H), 1.63 (dt, J¼14.26, 6.90 Hz, 2H), 1.38e1.15 (m, 10H), 0.88 (t,
J¼7.05 Hz, 2H); 13C NMR: (125 MHz, acetone-d6)
d 145.7, 134.6,
130.9, 128.7, 83.5, 71.6, 32.9, 32.5, 26.1, 25.3, 25.29, 25.25, 24.8, 23.3,
21.5, 14.4; 11B NMR (128.4 MHz, acetone-d6)
d
6.03; 19F NMR
(470.8 MHz, acetone-d6)
d
ꢁ136.81; IR (cmꢁ1): 2916, 2850, 1362,
A 50 mL round-bottomed flask was charged with [Ir(cod)Cl]2
(50 mg, 0.074 mmol), dppe (59 mg, 0.148 mmol), and a stir bar in
1175, 1095, 964, 944, 835, 810, 720, 669, 650; HRMS (ESI) m/z cal-
culated for C15H23BF3O3S (MꢁKþ)þ: 351.1413, found: 351.1406.

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J. Lee, M.M. Joullie / Tetrahedron 71 (2015) 7620e7629
7625
4.4. Potassium trifluoro(10-(tosyloxy)decyl)borate (4)11
4.7. 5-(3-Hydroxypropyl)2,3-dihydro-1H-inden-1-one (7)
General procedure A was followed to obtain the title compound,
4.7.1. General procedure B. A microwave tube was charged with 5-
chloro-1-indanone (50 mg, 0.3 mmol), 1 (50.3 mg, 0.303 mmol),
Pd(OAc)2 (1.3 mg, 0.006 mmol), RuPhos (5.6 mg, 0.012 mmol),
K2CO3 (124 mg, 0.9 mmol), and a stir bar. The cap was sealed, and
evacuated and purged with Ar (3 cycles). Degassed toluene:H2O
mixture (1.2 mL) was then added to the microwave tube via syringe
and the resulting reaction mixture was heated to 90 ꢀC for 36 h (For
larger scale operation, the reaction was set up in a glove box.) H2O
(1 mL) was added to the reaction, stirred for 5 min, and the
resulting layers were separated. The aqueous layer was extracted
with ethyl acetate (2 mL, three times). The organic layers were
combined, dried over Na2SO4, filtered, and concentrated. Purifica-
tion by silica gel chromatography (50% EtOAc/Hexanes) afforded
the coupled product 7 in 84% yield as an amorphous solid. Rf 0.21
which was characterized in our previous report.11 1H NMR and 13
C
NMR spectra obtained were in good agreement with the reported
spectra: 1H NMR: (500 MHz, acetone-d6)
d
7.84e7.81 (m, 2H),
7.52e7.49 (m, 2H), 4.06 (dt, J¼10.63, 5.0 Hz, 2H), 2.47 (s, 3H),
1.66e1.60 (m, 2H), 1.29e1.18 (m, 14H), 0.15e0.12 (m, 2H); 13C NMR:
(125 MHz, acetone-d6)
d 145.8, 134.5, 130.9, 128.7, 74.8, 71.6, 34.6,
30.8, 30.5, 26.6, 26.1, 25.3, 25.2, 21.6.
4.5. Potassium trifluoro(12-(tosyloxy)dodecyl)borate (5)
General procedure A was followed using the known corre-
sponding tosylate (1-(tosyloxy)dodec-11-ene)21 in the first step
and 12-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)dodecyl 4-
methylbenzenesulfonate (39) in the second step: Colourless oil.
(50% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d 7.69e7.68 (m, 1H),
7.32e7.29 (m, 1H), 7.21 (d, J¼7.82 Hz, 1H), 3.70 (t, J¼6.33 Hz, 2H),
3.11 (t, J¼5.84 Hz, 2H), 2.81 (t, J¼7.74 Hz, 2H), 2.68 (dd, J¼7.75,
3.98 Hz, 2H), 1.96e1.91 (m, 2H), 1.85e1.77 (m, 1H); 13C NMR:
(125 MHz, CDCl3) 206.7, 155.8, 149.8, 135.2, 128.0, 126.5, 123.7, 61.9,
36.4, 33.9, 32.5, 25.7; IR (cmꢁ1): 3413, 2929, 2864, 1705, 1609, 1438,
1404, 1332, 1288, 1246, 1231, 1104, 1056, 1033, 834, 815; HRMS (ESI)
m/z calculated for C12H14O2 (MþH)þ: 191.1071, found: 191.1072.
Rf 0.34 (10% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d 7.72 (d,
J¼8.32 Hz, 2H), 7.32 (d, J¼8.51 Hz, 2H), 4.00 (t, J¼6.54 Hz, 2H), 2.43
(s, 3H), 1.61 (dt, J¼14.43, 7.00 Hz, 2H), 1.40e1.17 (m, 30H), 0.74 (t,
J¼7.77, 2H); 13C NMR: (125 MHz, CDCl3)
d 144.4, 133.2, 129.6, 127.7,
82.7, 70.5, 32.2, 29.5. 29.4, 29.3, 29.2, 28.8, 28.7, 25.2, 24.7, 23.8,
21.4; 11B NMR (128.4 MHz, CDCl3)
d
33.68; IR (cmꢁ1): 2977, 2925,
2853, 1598, 1466, 1364, 1319, 1212, 1188, 1176, 1145, 1098, 1019, 966,
912, 846, 814, 790, 763, 732, 688, 665, 651, 641, 625; HRMS (ESI) m/z
calculated for C25H43BO5S (MþNa)þ: 489.2822, found: 489.2825.
The desired potassium alkyl trifluoroborate salt (5) was obtained in
88% yield: White solid. mp>200 ꢀC. 1H NMR: (500 MHz, DMSO-d6)
4.8. 5-(1-Oxo-2,3-dihydro-1H-inden-5-yl)pentyl 4-
methylbenzenesulfonate (8)
General procedure B was followed using 2 to afford the desired
compound in 70% yield. Yellow amorphous solid. Rf 0.23 (20%
d
7.78 (d, J¼8.1 Hz, 2H), 7.49 (d, J¼7.9 Hz, 2H), 4.00 (t, J¼6.2 Hz, 2H),
2.43 (s, 3H), 1.53 (t, J¼6.7 Hz, 2H), 1.19 (s, 18H), ꢁ0.04 to 0.10 (m,
2H); 13C NMR: (125 MHz, DMSO-d6)
144.8,132.5,130.1,127.5, 70.8,
33.1, 29.4, 29.2, 29.1, 28.9, 28.8, 28.1, 28.0, 25.6, 24.6, 21.0; 11B NMR
EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d
7.78 (d, J¼8.30 Hz, 2H),
d
7.67 (d, J¼7.85 Hz, 1H), 7.36e7.34 (m, 2H), 7.25 (s, 1H), 7.15 (d,
J¼7.86 Hz, 1H), 4.03 (t, J¼6.41 Hz, 2H), 3.11 (t, J¼5.86 Hz, 2H),
2.70e2.65 (m, 4H), 2.45 (s, 3H), 1.76e1.59 (m, 4H), 1.45e1.36 (m.
2H); 13C NMR: (125 MHz, CDCl3) 206.5, 155.7, 149.8, 144.6, 135.1,
133.1, 129.7, 127.9, 127.8, 126.8, 123.6, 70.2, 36.8, 36.0, 30.4, 28.6,
25.6, 24.9, 21.6; IR (cmꢁ1): 2932, 2860, 1708, 1608, 1494, 1440, 1403,
1357, 1281, 1188, 1176, 1097, 1030, 948, 903, 815, 663, 576, 554;
HRMS (ESI) m/z calculated for C21H24O4S (MþH)þ: 373.1474, found:
373.1473.
(128.4 MHz, DMSO-d6)
d
6.42; 19F NMR (470.8 MHz, DMSO-d6)
d
ꢁ136.82; IR (cmꢁ1): 2917, 2850, 1598, 1468, 1363, 1298, 1248, 1188,
1175, 1096, 1021, 965, 946, 918, 836, 809, 793, 720, 669, 642, 626.
HRMS (ESI) m/z calculated for C19H31BF3O3S (MꢁKþ)þ: 407.2042,
found: 407.2039.
4.6. Potassium trifluoro(14-(tosyloxy)tetradecyl)borate (6)
General procedure A was followed using tetradec-13-en-1-yl
4.9. 8-(1-Oxo-2,3-dihydro-1H-inden-5-yl)octyl 4-
4-methylbenzenesulfonate (35) in the first step and 14-
methylbenzenesulfonate (9)
(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)tetradecyl
methylbenzenesulfonate (40) in the second step: Colourless
oil. Rf 0.67 (20% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
7.80
4-
General procedure B was followed using 3 to afford the desired
compound in 65% yield. Yellow amorphous solid. Rf 0.24 (20%
d
(d, J¼7.80 Hz, 2H), 7.35 (d, J¼7.98 Hz, 2H), 4.05e4.02 (m, 2H),
2.46 (s, 3H), 1.67e1.61 (m, 2H), 1.41 (ddd, J¼12.36, 6.78, 6.30 Hz,
2H), 1.30e1.22 (m, 32H), 0.77 (t, J¼7.75 Hz, 2H); 13C NMR:
EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d
7.80 (d, J¼8.2 Hz, 2H),
7.68 (d, J¼7.8 Hz, 1H), 7.35 (d, J¼8.2 Hz, 2H), 7.19 (d, J¼7.9 Hz, 1H),
4.03 (t, J¼6.5 Hz, 2H), 3.12 (t, J¼5.9 Hz, 2H), 2.68 (dd, J¼10.3, 4.8 Hz,
(125 MHz, CDCl3)
d
144.5, 133.3, 129.7, 129.5, 127.8, 127.0, 82.8,
4H), 2.46 (s, 3H), 1.64 (dq, J¼14.4, 7.2 Hz, 4H), 1.35e1.25 (m, 9H); 13
C
70.6, 41.9, 32.4, 29.6, 29.58, 29.55, 29.4, 29.38, 29.36, 28.9, 28.7,
25.3, 24.7, 23.9, 21.5, 14.1; IR (cmꢁ1): 2977, 2925, 2854, 1598,
1466, 1367, 1321, 1188, 1177, 1145, 1097, 1020, 966, 814, 714, 663,
577, 554; HRMS (ESI) m/z calculated for C27H47BO5S (MþH)þ:
494.3316, found: 495.3318. The desired potassium alkyl tri-
fluoroborate salt (6) was obtained in 60% yield: White solid.
NMR: (125 MHz, CDCl3) 206.5, 155.6, 150.5, 144.5, 135.0, 133.2,
129.7, 127.9, 127.8, 126.3, 123.5, 70.5, 36.3, 36.2, 31.1, 29.1, 29.0, 28.8,
28.7, 25; 6, 25.2, 21.5; IR (cmꢁ1): 2928, 2856, 1709, 1608, 1495, 1441,
1403, 1359, 1289, 1229, 1188, 1176, 1097, 1030, 941, 815, 664, 577,
555; HRMS (ESI) m/z calculated for C24H30O4S (MþH)þ: 414.1943,
found: 414.1943.
mp>200 ꢀC. 1H NMR: (500 MHz, DMSO-d6)
d
7.78 (d, J¼8.2 Hz,
2H), 7.48 (d, J¼7.8 Hz, 2H), 4.00 (t, J¼6.3 Hz, 2H), 2.42 (s, 3H),
4.10. 10-(1-Oxo-2,3-dihydro-1H-inden-5-yl)decyl 4-
1.57e1.52 (m, 2H), 1.21e1.16 (m, 22H), ꢁ0.06 to 0.12 (m, 2H); 13C
methylbenzenesulfonate (10)11
NMR: (125 MHz, DMSO-d6)
d 144.7, 132.5, 130.1, 127.5, 89.7, 84.5,
70.8, 33.1, 29.4, 29.2, 29.1, 29.0, 28.9, 28.8, 28.7, 28.1, 28.0, 25.6,
General procedure B was followed to obtain the title compound
24.9, 24.6, 21.0; 11B NMR (128.4 MHz, acetone)
d
4.63; 19F NMR
in 70% yield, which was characterized in our previous report.11 1
H
(470.8 MHz, DMSO-d6)
d
ꢁ136.83; IR (cmꢁ1): 2916, 2850, 1364,
NMR and 13C NMR spectra obtained were in good agreement with
the reported spectra: 1H NMR: (500 MHz, CDCl3)
7.70, (d,
1176, 1095, 965, 923, 835, 809, 793, 719, 670. HRMS (ESI) m/z
calculated for C21H35BO3F3SK (MeF)þ(CH3O$)e: 447.2561, found:
447.2552.
d
J¼8.27 Hz, 2H), 7.64 (d, J¼7.85 Hz, 1H), 7.32 (d, J¼8.29 Hz, 2H), 7.26
(s, 1H), 7.17 (d, J¼7.85 Hz, 1H), 4.00 (t, J¼6.50 Hz, 2H), 3.08 (t,

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J. Lee, M.M. Joullie / Tetrahedron 71 (2015) 7620e7629
7626
J¼5.82 Hz, 2H), 2.68e2.64 (m, 4H), 2.42 (s, 3H), 1.65 (dt, J¼14.25,
6.95 Hz, 4H), 1.29e1.21 (m, 12H); 13C NMR: (125 MHz, CDCl3) 206.5,
155.6,150.6,144.5,134.8,133.0,129.6,127.8,127.6,126.2,123.3, 70.5,
36.3, 36.2, 31.1, 29.2, 29.1, 29.0, 28.7, 28.6, 25.5, 25.1, 21.4.
combined, washed with brine (100 mL), dried over Na2SO4, filtered,
and concentrated. Purification by silica gel chromatography (25%
EtOAc/Hexanes) afforded 14 in 91% yield as a yellow oil. Rf 0.39 (20%
EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d
7.65 (d, J¼7.8 Hz,1H), 7.26
(s, 1H), 7.16 (dd, J¼7.8, 0.6 Hz, 1H), 3.09 (t, J¼5.9 Hz, 2H), 2.84 (t,
J¼7.3 Hz, 2H), 2.69e2.64 (m, 4H), 2.30 (s, 3H), 1.68e1.56 (m, 4H),
1.43e1.37 (m, 2H); 13C NMR: (125 MHz, CDCl3) 206.6, 195.9, 155.7,
150.2, 135.1, 127.9, 126.4, 123.6, 36.4, 36.1, 30.68, 30.63, 29.3, 28.9,
28.3, 25.7; IR (cmꢁ1): 2930, 2857, 1710, 1608, 1435, 1353, 1330,1284,
1230, 1134, 1104, 1030, 956, 813, 627, 586; HRMS (ESI) m/z calcu-
lated for C16H20O2S (MþH)þ: 277.1262, found: 277.1264.
4.11. 12-(1-Oxo-2,3-dihydro-1H-inden-5-yl)dodecyl 4-
methylbenzenesulfonate (11)
General procedure B was followed using 5 to afford the desired
compound in 38% yield. White amorphous solid. Rf 0.39 (20%
EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d
7.80 (d, J¼8.0 Hz, 2H),
7.68 (d, J¼7.9 Hz, 1H), 7.35 (d, J¼8.2 Hz, 2H), 7.20 (d, J¼7.8 Hz, 1H),
4.04e4.02 (m, 2H), 3.12 (t, J¼5.8 Hz, 2H), 2.71e2.68 (m, 4H), 2.46 (s,
3H), 1.69e1.62 (m, 4H), 1.32e1.23 (m, 17H); 13C NMR: (125 MHz,
CDCl3) 206.6, 155.6, 150.7, 144.5, 135.0, 133.2, 129.7, 127.9, 127.8,
126.3, 123.5, 70.6, 36.3, 31.2, 29.5, 29.45, 29.4, 29.3, 29.2, 28.8, 28.7,
25.6, 25.2, 21.5; IR (cmꢁ1): 2977, 2922, 2849, 1704, 1607, 1470, 1434,
1393, 1356, 1323, 1296, 1281, 1246, 1186, 1173, 1097, 1030, 949, 837,
815, 670, 576, 556, 532; HRMS (ESI) m/z calculated for C28H38O4S
(MþH)þ: 471.2569, found: 471.2550.
4.15. S-(8-(1-Oxo-2,3-dihydro-1H-inden-5-yl)octyl) ethane-
thioate (15)
General procedure C was followed using 9 to afford the desired
compound in 98% yield. Yellow oil. Rf 0.65 (30% EtOAc/Hex); 1H
NMR: (500 MHz, CDCl3)
d
7.65 (d, J¼7.8 Hz, 1H), 7.26 (s, 1H), 7.17 (d,
J¼7.8 Hz, 1H), 3.09 (t, J¼5.7 Hz, 2H), 2.84 (t, J¼7.3 Hz, 2H), 2.66 (q,
J¼6.7 Hz, 4H), 2.30 (s, 3H), 1.62 (q, J¼7.1 Hz, 2H), 1.55 (quintet,
J¼7.2 Hz, 2H), 1.31e1.23 (m, 8H); 13C NMR: (125 MHz, CDCl3) 206.3,
195.7, 155.5, 150.4, 134.9, 127.8, 126.2, 123.4, 36.3, 36.2, 31.0, 30.4,
30.0, 29.3, 29.1, 29.0, 28.9, 28.8, 28.5, 25.5; IR (cmꢁ1): 3009, 2926,
2854, 1694, 1608, 1439, 1353, 1330, 1282, 1245, 1230, 1192, 1133,
1105, 1030, 954, 886, 835, 814, 763, 724, 673, 627, 586; HRMS (ESI)
m/z calculated for C19H26O2S (MþH)þ: 319.1732, found: 319.1729.
4.12. 14-(1-Oxo-2,3-dihydro-1H-inden-5-yl)tetradecyl 4-
methylbenzenesulfonate (12)
General procedure B was followed using 6 to afford the desired
compound in 51% yield. White amorphous solid. Rf 0.45 (20% EtOAc/
Hex); 1H NMR: (500 MHz, CDCl3)
d
7.79 (d, J¼8.3 Hz, 2H), 7.67 (d,
J¼7.8 Hz, 1H), 7.36e7.34 (m, 2H), 7.28 (d, J¼0.8 Hz, 1H), 7.19 (d,
J¼7.9 Hz, 1H), 4.02 (t, J¼6.5 Hz, 2H), 3.11 (t, J¼5.9 Hz, 2H), 2.71e2.67
(m, 4H), 2.45 (s, 3H), 1.69e1.59 (m, 6H), 1.36e1.18 (m, 18H); 13C
NMR: (125 MHz, CDCl3) 206.6, 155.6, 150.7, 144.5, 134.9,133.1, 129.7,
127.9, 126.3, 123.4, 70.6, 36.3, 31.2, 29.6, 29.5, 29.47, 29.41, 29.39,
29.3, 29.2, 28.8, 28.7, 25.6, 25.2, 21.5; IR (cmꢁ1): 2917, 2851, 1712,
1607, 1472, 1433, 1360, 1228, 1186, 1171, 1095, 1030, 977, 955, 832,
807, 794, 719, 689, 668, 644; HRMS (ESI) m/z calculated for
4.16. S-(10-(1-Oxo-2,3-dihydro-1H-inden-5-yl)decyl) ethane-
thioate (16)11
General procedure C was followed to obtain the title compound
in 84% yield, which was characterized in our previous report.11 1
H
NMR and 13C NMR spectra obtained were in good agreement with
the reported spectra: 1H NMR: (500 MHz, CDCl3)
d
7.67 (d, J¼7.9 Hz,
1H), 7.28 (s, 1H), 7.19 (d, J¼7.9 Hz, 1H), 3.11 (t, J¼5.8 Hz, 2H), 2.86 (t,
J¼7.4 Hz, 2H), 2.69e2.66 (m, 4H), 2.32 (s, 3H), 1.63 (dt, J¼14.7,
7.4 Hz, 2H), 1.56 (dq, J¼14.3, 7.0 Hz, 2H), 1.31 (dd, J¼21.5, 15.0 Hz,
10H); 13C NMR: (125 MHz, CDCl3) 206.5, 195.9, 155.6, 150.6, 134.9,
127.9, 126.2, 123.4, 36.3, 31.2, 30.5, 29.4, 29.3, 29.1, 29.0, 28.9, 28.7,
25.6.
C
30H42O4S (MþNa)þ: 521.2702, found: 521.2698.
4.13. S-(3-(1-Oxo-2,3-dihydro-1H-inden-5-yl)propyl) ethane-
thioate (13)
To a stirred solution of 7 (48 mg, 0.252 mmol) in anhydrous THF
(2.5 mL) was added triphenylphosphine (99 mg, 0.378 mmol),
4.17. S-(12-(1-Oxo-2,3-dihydro-1H-inden-5-yl)dodecyl) etha-
diethyl azodicarboxylate (60
m
L, 0.378 mmol), and thioacetic acid
nethioate (17)
(36 L, 0.505 mmol). The resulting mixture was left to stir at room
m
temperature for 20 h. Upon completion, the reaction mixture was
concentrated under vacuum to afford the crude product as a yellow
oil. Purification by silica gel chromatography (30% EtOAc/Hexanes)
afforded 13 as a yellow oil (53 mg, 84%). Rf 0.51 (30% EtOAc/Hex); 1H
General procedure C was followed using 11 to afford the desired
compound in 93% yield. Amorphous solid. Rf 0.63 (20% EtOAc/Hex);
1H NMR: (500 MHz, CDCl3)
d
7.69 (d, J¼7.8 Hz, 1H), 7.29 (s, 1H), 7.21
(d, J¼7.8 Hz, 1H), 3.13 (dd, J¼7.6, 4.1 Hz, 2H), 2.88 (t, J¼7.4 Hz, 2H),
2.72e2.69 (m, 4H), 2.34 (s, 3H), 1.72e1.62 (m, 2H), 1.61e1.54 (m,
2H), 1.37e1.28 (m, 16H); 13C NMR: (125 MHz, CDCl3) 206.6, 196.0,
155.6, 150.7, 135.0, 128.0, 126.3, 123.5, 36.4, 31.2, 30.6, 29.6, 29.5,
29.49, 29.43, 29.2, 29.1, 29.0, 28.8, 25.7; IR (cmꢁ1): 2917, 2851, 1701,
1686, 1607, 1470, 1443, 1352, 1334, 1295, 1273, 1231, 1193, 1135,
1106, 1031, 959, 903, 818, 766, 719, 639; HRMS (ESI) m/z calculated
for C23H34O2S (MþNa)þ: 397.2177, found: 397.2177.
NMR: (500 MHz, CDCl3)
d
7.68 (dd, J¼7.8, 1.5 Hz, 1H), 7.29 (s, 1H),
7.19 (d, J¼7.8 Hz, 1H), 3.11 (t, J¼5.4 Hz, 2H), 2.90 (td, J¼7.2, 1.7 Hz,
2H), 2.79e2.76 (m, 2H), 2.70e2.67 (m, 2H), 2.35 (d, J¼2.1 Hz, 3H),
1.97e1.91 (m, 2H); 13C NMR: (125 MHz, CDCl3) 206.5, 195.6, 155.8,
148.8, 135.4, 128.0, 126.5, 123.8, 36.4, 35.2, 31.0, 30.7, 28.5, 25.7; IR
(cmꢁ1): 2925, 2859, 1709, 1609, 1439, 1354, 1331, 1281, 1230, 1134,
1103, 1032, 953, 837, 815, 626; HRMS (ESI) m/z calculated for
C
14H16O2S (MþNa)þ: 271.0762, found: 271.0769.
4.18. S-(14-(1-Oxo-2,3-dihydro-1H-inden-5-yl)tetradecyl)
4.14. S-(5-(1-Oxo-2,3-dihydro-1H-inden-5-yl)pentyl) ethane-
ethanethioate (18)
thioate (14)
General procedure C was followed using 12 to afford the desired
compound in 94% yield. Amorphous solid. Rf 0.5 (20% EtOAc/Hex);
4.14.1. General procedure C. To a stirred solution of 8 (780 mg,
2.09 mmol) in anhydrous acetonitrile (131 mL) was added potas-
sium thioacetate (478 mg, 4.19 mmol) in one portion. The resulting
mixture was then brought to 60 ꢀC and left to stir overnight. The
reaction was quenched by addition of H2O (100 mL), and extracted
with CH2Cl2 (100 mL, three times). Organic layers were then
1H NMR: (500 MHz, CDCl3)
d
7.69 (d, J¼7.8 Hz, 1H), 7.29 (s, 1H), 7.21
(d, J¼7.8 Hz, 1H), 3.12 (dd, J¼5.9, 5.7 Hz, 2H), 2.88 (t, J¼7.4 Hz, 2H),
2.71e2.69 (m, 4H), 2.34 (s, 3H), 1.71e1.62 (m, 2H), 1.61e1.55 (m,
4H), 1.38e1.27 (m, 18H); 13C NMR: (125 MHz, CDCl3) 206.6, 196.0,
155.6, 150.8, 135.0, 128.0, 126.3, 123.5, 36.4, 31.3, 30.6, 29.6, 29.56,

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J. Lee, M.M. Joullie / Tetrahedron 71 (2015) 7620e7629
7627
29.53, 29.49, 29.46, 29.2, 29.15, 29.11, 28.8, 25.7; IR (cmꢁ1): 2916,
2849, 1701, 1686, 1607, 1469, 1442, 1428, 1234, 1120, 1030, 958, 818,
654; HRMS (ESI) m/z calculated for C25H38O2S (MþNa)þ: 425.2490,
found: 425.2498.
J¼7.9 Hz, 1H), 7.33 (s, 1H), 7.26 (d, J¼7.9 Hz, 1H), 3.85 (s, 2H), 2.87 (t,
J¼7.4 Hz, 2H), 2.71 (t, J¼7.7 Hz, 2H), 2.34 (s, 3H), 1.66 (dq, J¼13.8,
6.9 Hz, 3H), 1.60e1.54 (m, 3H), 1.34e1.28 (m, 11H); 13C NMR:
(125 MHz, CDCl3) 196.2, 189.2, 155.3, 152.8, 147.3, 135.6, 128.7, 126.4,
124.5, 36.6, 31.1, 30.6, 29.4, 29.37, 29.34, 29.2, 29.1, 29.0, 28.7, 28.2.
4.19. S-(3-(2-(Hydroxyimino)-1-oxo-2,3-dihydro-1H-inden-5-
yl)propyl) ethanethioate (19)
4.23. S-(12-(2-(Hydroxyimino)-1-oxo-2,3-dihydro-1H-inden-
5-yl)dodecyl) ethanethioate (23)
4.19.1. General procedure D. To a stirred solution of 13 (53 mg,
0.213 mmol) in anhydrous CH2Cl2 (0.85 mL) atꢁ20 ꢀC was added
General procedure D was followed using 17 to afford the desired
compound in quantitative yield. Off-white amorphous solid. Rf 0.5
TMSCl (27
mL, 0.213 mmol) followed by drop-wise addition of iso-
amy nitrite (29
mL, 0.213 mmol). The resulting mixture was left to
(40% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d
7.82 (d, J¼7.9 Hz,
stir at ꢁ20 ꢀC for 1 h. The reaction was quenched by addition of H2O
(1 mL), and the layers were separated. The aqueous layer was
extracted with CH2Cl2 (3 mL, three times), and the organic layers
were combined. The organic layer was washed with brine (1 mL),
dried over MgSO4, filtered, and concentrated to afford the oxime 19
in quantitative yield as an off-white amorphous solid. Rf 0.18 (40%
1H), 7.34 (s, 1H), 7.26 (s, 1H), 3.85 (s, 2H), 2.88 (t, J¼7.4 Hz, 2H), 2.72
(t, J¼7.7 Hz, 2H), 2.34 (s, 3H), 1.70e1.64 (m, 2H), 1.60e1.54 (m, 2H),
1.36e1.27 (m, 17H); 13C NMR: (125 MHz, CDCl3) 196.2, 189.0, 155.4,
152.7, 147.2, 135.7, 128.7, 126.4, 124.5, 36.6, 31.1, 30.6, 29.53, 29.5,
29.46, 29.42, 29.3, 29.2, 29.1, 29.0, 28.7, 28.2; IR (cmꢁ1): 3258, 2916,
2851, 1726, 1685, 1655, 1610, 1581, 1470, 1406, 1353, 1332, 1303,
1272, 1113, 1037, 960, 922, 906, 832, 755, 756, 689, 640; HRMS (ESI)
EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d
7.82 (d, J¼7.9 Hz,1H), 7.35
(s, 1H), 7.28 (s, 1H), 3.85 (s, 2H), 2.92 (t, J¼7.2 Hz, 2H), 2.81 (dd,
m/z calculated for
426.2081.
C
23H33NO3S (MþNa)þ: 426.2079, found:
J¼9.9, 5.4 Hz, 2H), 2.37 (s, 3H), 1.97 (dt, J¼14.9, 7.4 Hz, 2H); 13C
NMR: (125 MHz, CDCl3)
d 195.9, 189.05, 155.3, 150.9, 147.4, 136.0,
128.7, 126.6, 124.8, 35.5, 30.83, 30.68, 28.47, 28.31; IR (cmꢁ1): 3250,
2938, 1729, 1689, 1656, 1614, 1438, 1407, 1350, 1333, 1304, 1293,
1274, 1141, 1108, 1040, 947, 925, 907, 833, 774, 763, 730, 691, 629;
HRMS (ESI) m/z calculated for C14H15NO3S (MþH)þ: 278.0850,
found: 278.0851.
4.24. S-(14-(2-(Hydroxyimino)-1-oxo-2,3-dihydro-1H-inden-
5-yl)tetradecyl) ethanethioate (24)
General procedure D was followed using 18 to afford the desired
compound in quantitative yield. Off-white amorphous solid. Rf 0.53
(40% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d
7.81 (d, J¼7.8 Hz,
4.20. S-(5-(2-(Hydroxyimino)-1-oxo-2,3-dihydro-1H-inden-5-
yl)pentyl) ethanethioate (20)
1H), 7.33 (s, 1H), 7.28 (d, J¼2.7 Hz, 1H), 3.85 (s, 2H), 2.87 (t, J¼7.2 Hz,
2H), 2.72 (t, J¼7.3 Hz, 2H), 2.33 (s, 3H), 1.67e1.63 (m, 2H), 1.60e1.54
(m, 2H), 1.34e1.32 (m, 21H); 13C NMR: (125 MHz, CDCl3) 196.2,
189.1, 155.3, 152.7, 147.3, 135.7, 128.7, 126.4, 124.5, 36.6, 31.1, 30.6,
29.57, 29.53, 29.4, 29.3, 29.2, 29.1, 29.0, 28.7, 28.2; IR (cmꢁ1): 3252,
2916, 2849, 1726, 1685, 1655, 1609, 1470, 1435, 1353, 1332, 1303,
1270, 1139, 1120, 1037, 959, 923, 907, 833, 774, 754, 690, 663, 639;
HRMS (ESI) m/z calculated for C25H37NO3S (MþNa)þ: 454.2392,
found: 454.2387.
General procedure D was followed using 14 to afford the desired
compound in quantitative yield. Light yellow amorphous solid. Rf
0.3 (40% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d
7.82 (d, J¼7.9 Hz,
1H), 7.34 (s, 1H), 7.27 (d, J¼8.0 Hz, 1H), 3.85 (s, 2H), 2.88 (t, J¼7.3 Hz,
2H), 2.73 (t, J¼7.7 Hz, 2H), 2.34 (s, 3H), 1.73e1.60 (m, 5H), 1.47e1.42
(m, 2H); 13C NMR: (125 MHz, CDCl3)
d 196.1, 189.2, 155.4, 152.3,
147.4, 135.8, 128.7, 126.5, 124.7, 36.4, 30.67, 30.56, 29.3, 28.9, 28.32,
28.26; IR (cmꢁ1): 3497, 3386, 2925, 2858, 1707, 1688, 1649, 1608,
1491, 1340, 1279, 1139, 1112, 1043, 948, 922, 910, 843; HRMS (ESI)
4.25. S-(3-(1,2-Dioxo-2,3-dihydro-1H-inden-5-yl)propyl etha-
nethioate (25)
m/z calculated for
C
16H19NO3S (MþNa)þ: 328.0983, found:
328.0993.
4.25.1. General procedure E. To a stirred solution of 19 (30 mg,
0.108 mmol) in CH2Cl2 (1 mL) was added aqueous formaldehyde
4.21. S-(8-(2-(Hydroxyimino)-1-oxo-2,3-dihydro-1H-inden-5-
(37% in water, 48 mL) followed by conc. HCl (96 mL). The resulting
yl)octyl) ethanethioate (21)
mixture was stirred at room temperature overnight. The reaction
was quenched with cold H2O (1 mL), and the layers were separated.
The aqueous layer was extracted with CH2Cl2 (2 mL, three times),
and the organic layers were combined. The organic layer was
washed with brine (1 mL), dried over MgSO4, filtered, and con-
centrated to afford 25 and a minor amount of thioacetate removed
thiol, which was used without further purification. Light yellow
amorphous solid. Rf 0.3 (50% EtOAc/Hex); 1H NMR: (500 MHz,
General procedure D was followed using 15 to afford the desired
compound in quantitative yield. Light yellow amorphous solid. Rf
0.36 (40% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d 7.82 (d,
J¼7.9 Hz, 1H), 7.33 (s, 1H), 7.26 (d, J¼8.0 Hz, 1H), 3.85 (s, 2H), 2.87 (t,
J¼7.4 Hz, 2H), 2.72 (t, J¼7.7 Hz, 2H), 2.34 (s, 3H), 1.69e1.63 (m, 2H),
1.60e1.54 (m, 2H), 1.34e1.28 (m, 9H); 13C NMR: (125 MHz, CDCl3)
196.2, 189.0, 155.4, 152.6, 147.2, 135.7, 128.6, 126.4, 124.6, 36.6, 31.0,
30.6, 29.4, 29.2, 29.1, 29.0, 28.9, 28.6, 28.2; IR (cmꢁ1): 3247, 2922,
2852, 1726, 1686, 1655, 1608, 1469, 1434, 1407, 1332, 1302, 1273,
1126, 1109, 1037, 959, 946, 924, 905, 832, 773, 755, 691, 634; HRMS
(ESI) m/z calculated for C19H25NO3S (MþNa)þ: 370.1453, found:
370.1453.
CDCl3)
d
7.84 (d, J¼7.9 Hz, 1H), 7.39 (s, 1H), 7.32 (d, J¼7.8 Hz, 1H),
3.61 (s, 2H), 2.92 (t, J¼7.2 Hz, 2H), 2.83 (t, J¼7.7 Hz, 2H), 2.35 (s, 3H),
1.97 (dt, J¼14.9, 7.4 Hz, 2H); 13C NMR: (125 MHz, CDCl3)
d 200.2,
195.6, 186.5, 152.7, 147.0, 135.3, 129.3, 127.1, 125.8, 36.6, 35.7, 30.71,
30.67, 28.4; IR (cmꢁ1): 2923, 2853, 1765, 1719, 1688, 1610, 1438,
1391, 1354, 1329, 1298, 1262, 1204, 1135, 1121, 1090, 948, 835, 749,
669, 627, 566; HRMS (ESI) m/z calculated for C14H14O3S (MþNa)þ:
285.0570, found: 285.0561.
4.22. S-(10-(2-(Hydroxyimino)-1-oxo-2,3-dihydro-1H-inden-
5-yl)decyl) ethanethioate (22)11
4.26. S-(5-(1,2-Dioxo-2,3-dihydro-1H-inden-5-yl)pentyl etha-
General procedure D was followed to obtain the title compound
in quantitative yield, which was characterized in our previous re-
port.11 1H NMR and 13C NMR spectra obtained were in good agree-
nethioate (26)
General procedure E was followed using 20 to afford the desired
compound in quantitative yield. Yellow amorphous solid. Rf 0.52
ment with the reported spectra: 1H NMR: (500 MHz, CDCl3)
d 7.81 (d,

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J. Lee, M.M. Joullie / Tetrahedron 71 (2015) 7620e7629
7628
(40% EtOAc/Hex); 1H NMR: (500 MHz, CDCl3)
d
7.84 (d, J¼7.9 Hz,
1437,1385,1351,1328,1262,1118, 948, 823, 718, 630; HRMS (ESI) m/
1H), 7.37 (s, 1H), 7.31 (d, J¼7.9 Hz, 1H), 3.60 (s, 2H), 2.87 (t, J¼7.3 Hz,
2H), 2.75 (t, J¼7.7 Hz, 2H), 2.33 (s, 3H), 1.74e1.60 (m, 6H), 1.48e1.41
(m, 4H); 13C NMR: (125 MHz, CDCl3) 200.2, 195.8, 186.4, 154,0,
146.9, 135.1, 129.2, 126.9, 125.7, 36.6, 36.5, 30.5, 30.3, 29.2, 28.7,
28.2; IR (cmꢁ1): 2932, 2858, 1764, 1719, 1688, 1609, 1437,1391, 1353,
1263, 1134, 949, 837, 752, 627; HRMS (ESI) m/z calculated for
z calculated for C25H36O3S (MþNa)þ: 439.2283, found: 439.2278.
Acknowledgements
Financial support for this research was provided by the Uni-
versity of Pennsylvania, the National Science Foundation (NSF-CHE-
0951394), National Institute of Justice graduate research fellowship
(2012-IJ-CX-0019 to J.L.), and Novartis graduate research fellowship
in organic chemistry for minorities and women (to J.L.). We thank
Robert Ramotowski (FSD) and Antonio Cantu for helpful discus-
sions regarding the fingerprint visualization process. Dr. Simon
Berritt (University of Pennsylvania) is acknowledged for assistance
in manuscript preparation. Dr. George Furst and Dr. Rakesh Kohli
(University of Pennsylvania) are acknowledged for assistance in
NMR and MS respectively. Hongseok Yun and Dr. Taejong Paik,
(University of Pennsylvania) are gratefully acknowledged for as-
sistance in TEM and SEM imaging respectively.
C
16H18O3S (MþH)þ: 291.1055, found: 291.1060.
4.27. S-(8-(1,2-Dioxo-2,3-dihydro-1H-inden-5-yl)octyl etha-
nethioate (27)
General procedure E was followed using 21 to afford the desired
compound in quantitative yield. Yellow oil. Rf 0.6 (40% EtOAc/Hex);
1H NMR: (500 MHz, CDCl3)
d
7.83 (d, J¼7.9 Hz, 1H), 7.37 (s, 1H), 7.31
(d, J¼8.0 Hz, 1H), 3.60 (s, 2H), 2.85 (t, J¼7.4 Hz, 2H), 2.74 (t, J¼7.7 Hz,
2H), 2.32 (s, 3H), 1.70e1.64 (m, 3H), 1.56 (dt, J¼14.6, 7.3 Hz, 3H), 1.35
(dd, J¼13.3, 5.8 Hz, 6H); 13C NMR: (125 MHz, CDCl3) 200.3, 195.9,
186.4, 154.4, 146.8, 135.1, 129.2, 126.9, 125.6, 36.8, 36.5, 30.8, 30.5,
29.4, 29.1, 29.0, 28.9, 28.8, 28.6; IR (cmꢁ1): 3520, 2421, 3354, 3050,
2921, 2852, 2254, 1900, 1768, 1714, 1613, 1580, 1468, 1434, 1386,
1354, 1329, 1304, 1261, 1203, 1118, 1099, 951, 824, 755, 724, 667,
632; HRMS (ESI) m/z calculated for C19H24O3S (MþH)þ: 333.1524,
found: 333.1521.
Supplementary data
Supplementary data associated with this article can be found in
the online version, at http://dx.doi.org/10.1016/j.tet.2015.07.072.
References and notes
4.28. S-(10-(1,2-Dioxo-2,3-dihydro-1H-inden-5-yl)decyl etha-
nethioate (28)11
1. (a) Jelly, R.; Patton, E. L. T.; Lennard, C.; Lewis, S. W.; Lim, K. F. Anal. Chim. Acta
2009, 652, 128; (b) Lee, H. C.; Gaensslen, R. E. In Lee & Gaensslen’s Advances in
Fingerprint Technology, 3rd ed.; Ramotowski, R., Ed.; CRC: Boca Raton, 2013; (c)
General procedure E was followed to obtain the title compound
in quantitative yield, which was characterized in our previous re-
port.11 1H NMR and 13C NMR spectra obtained were in good
agreement with the reported spectra: 1H NMR: (500 MHz, CDCl3)
ꢀ
Hansen, D. B.; Joullie, M. M. Chem. Soc. Rev. 2005, 34, 408; (d) Becue, A.; Moret,
S.; Champod, C.; Margot, P. Biotech. Histochem. 2011, 86, 140; (e) Lennard, C.
Aust. J. Forensic Sci. 2014, 46, 293.
2. For ninhydrin: (a) Ruhemann, S. Trans. Chem. Soc. 1910, 97, 1438; (b) Oden, S.;
von Hofsten, B. Nature 1954, 173, 449; (c) Friedman, M.; Williams, L. D. Bioorg.
Chem. 1974, 3, 267; (d) Grigg, R.; Malone, J. F.; Mongkolaussavaratana, T.;
Thianpatanagul, S. J. Chem. Soc., Chem. Commun. 1986, 421 For 1,2-indanedione;
(e) Hauze, D. B.; Petrovskaia, O.; Taylor, B.; Joullie, M. M.; Ramotowski, R.;
Cantu, A. A. J. Forensic Sci. 1998, 43, 744; (f) Ramotowski, R.; Cantu, A. A.; Joullie,
ꢀ
d
7.86 (d, J¼7.9 Hz, 1H), 7.38 (s, 1H), 7.33 (d, J¼7.9 Hz, 1H), 3.61 (s,
2H), 2.89e2.86 (m, 2H), 2.76 (t, J¼7.7 Hz, 2H), 2.34 (s, 3H), 1.72e1.64
(m, 3H),1.62e1.54 (m, 3H),1.38e1.28 (m, 10H); 13C NMR: (125 MHz,
CDCl3) 200.3, 196.0, 186.4, 154.6, 146.8, 135.1, 129.2, 126.9, 125.7,
36.9, 36.6, 30.9, 30.6, 29.6, 29.4, 29.37, 29.34, 29.2, 29.1, 29.0, 28.7.
ꢀ
ꢀ
M. M.; Petrovskaia, O. Fingerprint Whorld 1997, 23, 131 For 1,8-diazafluoren-9-
one: (g) Grigg, R.; Mongkolaussavaratana, T.; Pounds, C. A.; Sivagnanam, S.
Tetrahedron Lett. 1990, 31, 7215.
3. Jaber, N.; Lesniewski, A.; Gabizon, H.; Shenawi, S.; Mandler, D.; Almog, J. Angew.
Chem., Int. Ed. 2012, 51, 12224.
4.29. S-(12-(1,2-Dioxo-2,3-dihydro-1H-inden-5-yl)dodecyl
ethanethioate (29)
4. (a) Choi, M. J.; McDonagh, A. M.; Maynard, P.; Roux, C. Forensic Sci. Int. 2008,
179, 87; (b) Dilag, J.; Kobus, H. J.; Ellis, A. V. Curr. Nanosci. 2011, 7, 153; (c) Sa-
metband, M.; Shweky, I.; Banin, U.; Mandler, D.; Almog, J. Chem. Commun. 2007,
1142; (d) He, Y.; Xu, L.; Zhu, Y.; Wei, Q.; Zhang, M.; Su, B. Angew. Chem., Int. Ed.
2014, 53, 12609.
5. (a) Cantu, A. A. Forensic Sci. Rev. 2001, 13, 29; (b) Burow, D.; Seifert, D.; Cantu, A.
A. J. Forensic Sci. 2003, 48, 1.
6. Selected references: (a) Saunders, G. In 74th Annual Educational Conference of
the International Association for Identification, Pensacola, FL, USA; 1989; (b)
Schnetz, B.; Margot, P. Forensic Sci. Int. 2001, 118, 21.
General procedure E was followed using 23 to afford the desired
compound in quantitative yield. Rf 0.71 (40% EtOAc/Hex); 1H NMR:
(500 MHz, CDCl3)
d
7.85 (d, J¼7.9 Hz, 1H), 7.38 (s, 1H), 7.33e7.32 (m,
1H), 3.61 (s, 2H), 2.87 (t, J¼7.3 Hz, 2H), 2.75 (t, J¼7.7 Hz, 2H), 2.34 (s,
3H), 1.71e1.65 (m, 3H), 1.60e1.54 (m, 3H), 1.36e1.27 (m, 14H); 13C
NMR: (125 MHz, CDCl3) 200.4, 196.0, 186.4, 154.6, 146.8, 135.1,
129.2, 126.9, 125.7, 36.9, 36.5, 30.9, 30.6, 29.5, 29.49, 29.45, 249.41,
29.3, 29.2, 29.1, 29.0, 28.7; IR (cmꢁ1): 2918, 2850, 1766, 1716, 1694,
1611, 1469, 1434, 1384, 1353, 1328, 1304, 1267, 1136, 1118, 951, 8223,
718, 630; HRMS (ESI) m/z calculated for C23H32O3S (MþNa)þ:
411.1970, found: 411.1973.
7. Selected references: (a) Stauffer, E.; Becue, A.; Singh, K. V.; Thampi, K. R.;
Champod, C.; Margot, P. Forensic Sci. Int. 2007, 168, e5; (b) Fairley, C.; Bleay, S.
M.; Sears, V. G.; NicDaeid, N. Forensic Sci. Int. 2012, 217, 5; (c) Moret, S.; Becue, A.
J. Forensic Ident. 2015, 65, 138.
ꢀ
8. Moret, S.; Becue, A.; Champod, C. Nanotechnology 2014, 25, 425502.
ꢀ
9. (a) Taylor, B. M.; Joullie, M. M. Tetrahedron 1998, 54, 15121; (b) Petrovskaia, O.;
ꢀ
Taylor, B. M.; Hauze, D. B.; Carroll, P. J.; Joullie, M. M. J. Org. Chem. 2001, 66,
7666.
10. Selected references: (a) Wallace-Kunkel, C.; Lennard, C.; Stoilovic, M.; Roux, C.
Forensic Sci. Int. 2007, 168, 14; (b) Spindler, X.; Shimmon, R.; Roux, C.; Lennard,
C. Forensic Sci. Int. 2011, 212, 150; (c) Marriott, C.; Lee, R.; Wilkes, Z.; Comber, B.;
Spindler, X.; Roux, C.; Lennard, C. Forensic Sci. Int. 2014, 236, 30.
4.30. S-(14-(1,2-Dioxo-2,3-dihydro-1H-inden-5-yl)tetradecyl
ethanethioate (30)
ꢀ
11. Lee, J.; Joullie, M. M. Tetrahedron Lett. 2015, 56, 3378.
12. Kotiaho, A.; Lahtinen, R.; Efimov, A.; Lehtivuori, H.; Tkachenko, N. V.; Kanerva,
General procedure E was followed using 24 to afford the desired
compound in quantitative yield. Rf 0.7 (40% EtOAc/Hex); 1H NMR:
T.; Lemmetyinen, H. J. Photochem. Photobiol., A 2010, 212, 129.
13. (a) Prasad, B. L. V.; Stoeva, S. I.; Sorensen, C. M.; Klabunde, K. J. Langmuir 2002,
18, 7515; (b) Sun, Y.; Jose, D.; Sorensen, C.; Klabunde, K. J. Nanomaterials 2013, 3,
370; (c) Moon, S. Y.; Tanaka, S.-I.; Sekino, T. Nanoscale Res. Lett. 2010, 5, 813.
14. (a) Amendola, V.; Meneghetti, M. J. Phys. Chem. C 2009, 113, 4277; (b) Storhoff,
J. J.; Lazarides, A. A.; Mucic, R. C.; Mirkin, C. A.; Letsinger, R. L.; Schatz, G. C. J. Am.
Chem. Soc. 2000, 122, 4640; (c) Taleb, A.; Petit, C.; Pileni, M. P. J. Phys. Chem. B
1998, 102, 2214.
(500 MHz, CDCl3)
d
7.85 (d, J¼8.0 Hz, 1H), 7.38 (s, 1H), 7.33 (d,
J¼8.0 Hz, 1H), 3.61 (s, 2H), 2.87 (t, J¼7.4 Hz, 2H), 2.75 (t, J¼7.7 Hz,
2H), 2.33 (s, 3H), 1.71e1.54 (m, 8H), 1.36e1.27 (m, 16H); 13C NMR:
(125 MHz, CDCl3) 200.4, 196.0, 186.4, 154.6, 146.8, 135.1, 129.2,
126.9,125.7, 36.9, 36.5, 30.9, 30.6, 29.6, 29.5, 29.47, 29.43, 29.3, 29.2,
29.1, 29.0, 28.7; IR (cmꢁ1): 2919, 2849, 1765, 1719, 1693, 1610, 1470,
15. (a) Bellino, M. G.; Calvo, E. J.; Gordillo, G. Phys. Chem. Chem. Phys. 2004, 6, 424;
(b) Baranov, D.; Kadnikova, E. N. J. Mater. Chem. 2011, 21, 6152; (c) Chegel, V.;

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J. Lee, M.M. Joullie / Tetrahedron 71 (2015) 7620e7629
7629
Rachkov, O.; Lopatynskyi, A.; Ishihara, S.; Yanchuk, I.; Nemoto, Y.; Hill, J. P.;
Ariga, K. J. Phys. Chem. C 2012, 116, 2683.
18. Becue, A.; Scoundrianos, A.; Moret, S. Forensic Sci. Int. 2012, 219, 39.
19. Bull, J. A.; Charette, A. B. J. Am. Chem. Soc. 2010, 132, 1895.
16. Shenawi, S.; Jaber, N.; Almog, J.; Mandler, D. Chem. Commun. 2013, 3688.
17. According to recent guidelines published by the International Fingerprint Re-
search Group (IFRG), the present optimized study is of Phase 2 (Optimisation &
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