Hypervalent Iodine as a Terminal Oxidant in Wacker-Type Oxidation of Terminal Olefins to Methyl Ketones

Article abstract of DOI:10.1021/acs.joc.6b00137

A mimic of the Wacker process for C=O bond formation in terminal olefins can be initiated by a combination of the Pd(II) and hypervalent iodine reagent, Dess-Martin periodinane to generate methyl ketones. This operationally simple and scalable method offers Markovnikov selectivity, has good functional group compatibility, and is mild and high yielding.

Full text of DOI:10.1021/acs.joc.6b00137

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Article
Hypervalent Iodine as Terminal Oxidant in Wacker-
type Oxidation of Terminal Olefins to Methyl Ketones
Dipali A. Chaudhari, and Rodney Agustinho Fernandes
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b00137 • Publication Date (Web): 04 Feb 2016
Downloaded from http://pubs.acs.org on February 11, 2016
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Hypervalent Iodine as Terminal Oxidant in Wacker-type Oxidation of Terminal
Olefins to Methyl Ketones
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Dipali A. Chaudhari and Rodney A. Fernandes*
Department of Chemistry, Indian Institute of Technology Bombay
Powai, Mumbai, 400076, Maharashtra, India
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E-mail: rfernand@chem.iitb.ac.in
ABSTRACT: A mimic of Wacker process for C=O bond formation in terminal olefins can be
initiated by a combination of Pd(II)/hypervalent iodine reagent, Dess-Martin periodinane (DMP) to
generate methyl ketones. This operationally simple and scalable method offers Markonikov
selectivity, has good functional group compatibility, is mild and high yielding.
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INTRODUCTION
The chemistry of polyvalent iodine compounds has experienced an unprecedented growth during the
last few decades. This rolling interest is mainly due to the remarkable oxidizing properties of
hypervalent iodine reagents, their benign environmental nature and commercial availability. From
the beginning of 1990s, the domain of oxidative transformation has witnessed a renaissance, in
particular, the pioneering contributions by Dess and Martin has triggered confidence on the potential
use of Dess-Martin Periodinane (DMP) as an oxidizing agent for the selective transformation of
alcohols to carbonyl compounds.1 DMP has emerged as a powerful and selective oxidant that affects
a plethora of oxidative transformations in synthetic organic chemistry. These include construction of
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an array of p-quinones from a variety of anilide systems,2 deoximation of aldoximes/ketoximes,3
oxidation of the Baylis–Hillman adducts to α-methylene-β-keto esters,4 synthesis of 2-alkynyl
propenals,5 oxidation of fluoroalkyl-substituted carbinols6 and acceleration of the Dess-Martin
oxidation of alcohols by water.7
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The selective transformation of terminal olefins into polar functional groups late in synthetic
sequences is a challenge and the outcome in most cases is substrate dependent.8 Over the last few
decades, substantial research interest has been focused on developing an alternative to the traditional
re-oxidant CuCl2 for Wacker oxidation, which mainly generates corrosive reaction media,
chlorinated byproducts and isomerization of double bond.9 The basis of this process popularized by
several research groups, lies in the C=C bond activation to generate methyl ketones.10-12 In most of
the cases, a terminal olefin has been used as feedstock material where a C=C bond gets oxidized to
the C-C=O bond. Despite the significant advances made in the greener side of the hypervalent iodine
chemistry,13,14 the application in approaches involving C=O bond formation from olefins is far less
realized. A good example to convert terminal olefins to α,β-unsaturated ketones was recently
reported by Bigi and White15 employing 2.0 equiv. of benzoquinone and 25 mol% of PhI(OAc)2
(Scheme 1, A). Use of benzoquinone in Wacker oxidation was well established before10a,12b,16 and
here too they realized that it is responsible for Wacker oxidation catalyzed by a palladium source.
The role of PhI(OAc)2 was therefore concluded to be that in dehydrogenation and not as terminal
oxidant. The information gathered during the course of development of terminal oxidants in Wacker
process in our group17 made us to hypothesize about additional modes of reactivity that could be
revealed through further explorations of DMP toward Wacker-type oxidation. These assumptions
proved fruitful, and herein we report the direct oxidation of terminal olefins into methyl ketones. We
planned to study Wacker-type oxidation for C=O bond formation under N2 atmosphere with
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palladium catalyst and cyclic λ5-iodanes (Scheme 1, B). The reaction system does not require
oxygen or any other additives.
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Scheme 1. Oxidation of Terminal Olefins to Methyl Ketones.
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RESULTS AND DISCUSSION
1-Tetradecene 1a was chosen as a model substrate to optimize the reaction conditions (Table 1).
We chose Pd(OAc)2 (5 mol%) and tested several iodine based oxidants (Table 1, entries 1-7). The
use of 1.2 equiv. of DMP with 5 mol% of Pd(OAc)2 in CH3CN:H2O (7:1) at 50 °C could produce
tetradecane-2-one 2a in 95% yield in 1 h reaction (Table 1, entry 2). However, lower yields were
observed in the case of other oxidising agents such as 2-iodoxybenzoic acid (IBX) and
(diacetoxyiodo)benzene [PhI(OAc)2] (Table 1, entries 1 and 3, respectively). Oxidation in presence
of granular iodine as well as mixture of I2:mCPBA (1:2, 1.5 equiv.) (Table 1, entries 4 and 5,
respectively) failed to deliver the methyl ketone, indicating molecular iodine to be unfit for this
oxidation. Iodosobenzene (PhIO) did not support the system and could produce only 12% of the
product 2a (entry 6). [Bis(trifluoroacetoxy)iodo]benzene (PIFA) could lead to the product 2a in 36%
yield (Table 1, entry 7). The performance of different Pd-catalysts was tested using DMP (1.2 equiv.,
Table 1, entries 8-13), which showed that Pd(OAc)2 to be the most suitable catalyst (entry 2).
Various solvent combinations like DMA, DMF, THF and DMSO with water were examined (Table
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1, entries 14-17). These solvent combinations did not improve the yields in comparison to
CH3CN:H2O mixture (7:1, entry 2). Effect of temperature on the reaction was studied (Table 1,
entries 18-21), which confirmed that 50 oC was optimum requirement (entry 2). Higher temperatures
may decompose DMP resulting in reduced yield. Screening of DMP concentration (Table 1, entries
22-27) showed that 1.2 equiv. of DMP (entry 2) was optimum. The catalytic version using 10-20
mol% of DMP required longer reaction time and delivered the methyl ketone product in lower yields
although the starting olefin was consumed (entries 26 and 27). Lowering of Pd(OAc)2 concentration
from 5 mol% to lower values also did not favor the reaction yields (entries 28 and 29). The reactions
without Pd catalyst or the oxidant did not work (entries 30 and 31). In all cases over oxidation to
unsaturated compounds like in the work by White et al.15 (Scheme 1, A) was not observed indicating
a good selectivity towards only Wacker oxidation with the reaction system in this work.
Table 1. Optimization of Reaction Conditions.a
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Pd-catalyst
(X mol %)
Oxidant
(Y equiv.)
Temp. Time
(oC)
(h)
Yield
(%)
Entry
Solvent
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5
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7
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9
Pd(OAc)2(5)
Pd(OAc)2(5)
Pd(OAc)2(5)
Pd(OAc)2(5)
Pd(OAc)2(5)
Pd(OAc)2(5)
Pd(OAc)2(5)
Pd(OTFA)2 (5)
PdCl2 (5)
IBX (1.2)
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
1.5
68
DMP (1.2)
PhI(OAc)2 (1.2)
I2 (1.2)
1
95
6
58
1
NRb
NRb
12
I2:mCPBA (1:2, 1.5) CH3CN:H2O (7:1) 50
1
PhIO (1.2)
PIFA (1.2)
DMP (1.2)
DMP (1.2)
DMP (1.2)
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
72
23
1
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48
1
79
10 Pd(dba)2 (5)
1
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PdCl2(CH3CN)2
(5)
11
DMP (1.2)
CH3CN:H2O (7:1) 50
1.5
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12 [PdCl(allyl)]2 (5) DMP (1.2)
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
1.5
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1.2
1.2
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NRb
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NRb
NRb
13 Pd-C (5)
DMP (1.2)
DMP (1.2)
DMP (1.2)
DMP (1.2)
DMP (1.2)
DMP (1.2)
DMP (1.2)
DMP (1.2)
DMP (1.2)
DMP (0.5)
DMP (1.0)
DMP (1.5)
DMP (2.0)
DMP (10 mol%)
DMP (20 mol%)
DMP (1.2)
DMP (1.2)
--
14 Pd(OAc)2(5)
15 Pd(OAc)2(5)
16 Pd(OAc)2(5)
17 Pd(OAc)2(5)
18 Pd(OAc)2(5)
19 Pd(OAc)2(5)
20 Pd(OAc)2(5)
21 Pd(OAc)2(5)
22 Pd(OAc)2(5)
23 Pd(OAc)2(5)
24 Pd(OAc)2(5)
25 Pd(OAc)2(5)
26 Pd(OAc)2(5)
27 Pd(OAc)2(5)
28 Pd(OAc)2(1)
29 Pd(OAc)2(2)
30 Pd(OAc)2(5)
DMA:H2O (7:1)
DMF:H2O (7:1)
THF:H2O (7:1)
DMSO:H2O (7:1)
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CH3CN:H2O (7:1) rt
CH3CN:H2O (7:1) 40
CH3CN:H2O (7:1) 65
CH3CN:H2O (7:1) 85
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
CH3CN:H2O (7:1) 50
1
2
1.5
1
1
12
7
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31
--
DMP (1.2)
a
All reactions were performed with olefin 1a (0.5 mmol), oxidant (10 mol%−2.0 equiv.), Pd-
catalyst (1−5 mol%), at T °C in solvent (4 mL) under N2.
b NR = No Reaction
The scope of the reaction was investigated by varying the olefins. Initially, various inactivated
long chain olefins were tested under the optimized condition (Table 2). 1-Tetradecene, 1-octene, 1-
pentene and 1-decene delivered the corresponding methyl ketones 2a-d in 72-95% yields (Table 2).
Terminal alpha, omega-dienes also reacted well with excellent selectivity giving diketones 2e (78%)
and 2f (80%). Methyl ketone synthesis was compatible with diverse functional groups such as
bromides 2g (79%), 2h (81%), benzoate 2i (77%), MOM 2j (65%), silyl 2k (87%), esters 2l (88%),
2m (84%), aldehyde 2n (80%) and acids 2o (75%) and 2p (77%) with complete Markonikov
selectivity and in good yields (Table 2). Olefin bearing primary OH group failed to give the product
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2q. There could be competing reactions from both olefin and OH groups which resulted in trail of
spots on TLC. Lowering of DMP concentration resulted in unused starting material even after
prolonged reaction time. However the secondary OH group containing olefin worked well giving 2r
in moderate 56% yield.
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Table 2. Wacker Type Oxidation of Aliphatic Terminal Olefins.a
aOlefin 1 (0.5 mmol), Pd(OAc)2 (5 mol%), DMP (1.2 equiv.), CH3CN:H2O (7:1, 4 mL), 50 C under N2. bSubstrate (0.5
mmol), Pd(OAc)2 (10 mol %), DMP (2.4 equiv), CH3CN:H2O (7:1, 4 mL), at 50 °C under N2
o
Styrenes are masked precursors for aryl methyl ketone synthesis via olefin oxidation. However
the olefinic bond is an activated system to be investigated for issues of regioselectivity. A number of
aryl substituted styrenes were screened for oxidation under present protocol (Table 3). Simple
styrene proved to be an excellent substrate for the generation of acetophenone 4a (86%). Varying the
substituents on the aromatic unit suggested that electronic parameters are contributing factors in the
Wacker-type oxidation reaction. With electron donor groups the yields of aryl methyl ketones was
quite good: 4b (85%), 4c (83%), 4d (85%), 4e (87%) and 4f (74%). Electron-withdrawing group
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such as nitro which deactivates the ring was found to decrease the efficiency of the reaction
considerably (4g, 65%). 4-Phenyl styrene and 2-vinyl naphthalene delivered the corresponding
methyl ketones 4h (72%) and 4i (61%) in good yields. Notably, the tolerance of halo substituent (4j,
78%) and heteroaromatic compounds 4k (76%), 4l (76%) and 4m (75%) allowed this protocol to be
viable for heteroaryl methyl ketone synthesis. In a couple of cases traces of aldehydes were
observed, but the amount was well below 2% by 1H NMR.
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Table 3. Wacker Type Oxidation of Styrenes.a
a Olefin 3 (0.5 mmol), Pd(OAc)2 (5 mol%), DMP (1.2 equiv.), CH3CN:H2O (7:1, 4 mL), 50 oC under N2
We next investigated different substrates with substituents at the allylic or homoallylic positions
such as cycloalkyl, tertiary alcohols, aryl ethers, esters, silyl, acetates, MOM, phthalimide and
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menthyl groups (Table 4). Many of these substrates show possible co-ordination of the neighboring
oxygen atom to the Lewis acidic palladium causing water attack through multiple pathways.18
Substrates with tertiary alcohol functionality at the homoallylic position failed to deliver the methyl
ketones 6a and 6b. O-Allyl salicylic acid delivered the methyl ketone 6c in 77% yield. Similarly bis-
allyl derivatives of salicylic acid (with ester and ether functionality) gave the diketones 6d and 6e in
77% and 76% yields, respectively. Primary allyl alcohols with various protecting groups delivered
methyl ketones in good yields: phenyl (6f, 84%), benzyl (6g, 83%), 4-tert-butylphenyl (6h, 75%), 2-
naphthyl (6i, 76%), 2-bromo-5-methoxy phenyl (6j, 81%), 4-methylbenzoyl (6k, 87%) and
nitrobenzoyl 6l (64%) and 6m (63%). Homoallyl alcohols with acetate, benzoate and benzyl
protections delivered the methyl ketones 6n (73%), 6o (81%), 6p (76%), 6q (80%), 6r (55%), 6s
(77%) and 6t (79%) in good yields and complete Markonikov selectivity. The acyloin products 6u
(77%), 6v (82%), 6w (80%) and 6x (73%) were obtained in good yields without the formation of
competitive aldehydes (by heteroatom directed effects). Fluorine substituent at the meta position in
5y worked well and offered the methyl ketone 6y in 76% yield. TBS protected β-hydroxy-γ-lactone
5z failed to deliver the ketone 6z under this protocol. Menthyl allyl ether was a sluggish substrate
and gave 6aa in 52% yield. γ,δ-Unsaturated ester worked efficiently and delivered the ketones 6ab
and 6ac in 66% yield each, respectively. Terminal unbranched allyl phthalimide offered methyl
ketone 6ad in a good yield of 79%.
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Table 4. Synthesis of Methyl Ketones from Substituted Allylic and Homoallylic Compounds.a
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a
Reaction conditions: Substrate (0.5 mmol), Pd(OAc)2 (5 mol%,), DMP (1.2 equiv.), CH3CN:H2O (7:1, 4
mL), at 50 °C under N2. b Substrate (0.5 mmol), Pd(OAc)2 (10 mol %), DMP (2.4 equiv), CH3CN:H2O (7:1,
4 mL), at 50 °C under N2. c NR = no reaction.
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The scale-up experiments on gram scale were attempted on terminal alpha omega-diene 1f,
styrene 3a and 4-pentenoic acid 1o. The reactions on 1 g scale of each delivered comparable results
as in tables 1 and 2 for these substrates giving 2f, 4a and 2o (levulinic acid) in 75%, 81% and 68%
isolated yields, respectively.
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Scheme 2. Gram Scale Reactions.
Iodine compounds in higher valence state are good oxidants.14b Similar to CuCl2 acting as oxidant
in the normal Wacker process we believe DMP serves as an oxidant for regeneration of Pd(II) from
Pd(0), although we could not ascertain the exact fate of DMP in the process. In comparison, the
iodine(III) reagents also worked as oxidants but delivered lower yields of the methyl ketones (Table
1). We could not isolate iodine (III) compounds or iodobenzoic acid after the reaction.
CONCLUSION
In conclusion we revealed here an efficient and general method to synthesize methyl ketones
employing cyclic λ5-iodane (Dess-Martin periodinane) reagent, mimicking the Wacker process.19
The objective to promote a direct and operationally simple oxidation process was achieved. Various
long chain terminal olefins, dienes, substituted styrenes, allyl and homoallyl alcohols with various
protecting groups have been explored (61 examples). A wide spectrum of functional-group
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tolerance, mild reaction conditions, Markonikov selectivity and use of commercially available Dess-
Martin periodinane as the sole oxidant are key features of this methodology. Since it is a process
with operational simplicity and exclusive ketone delivery, we expect this method to find broad
applications in synthetic chemistry.
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EXPERIMENTAL SECTION
General Information. 1H and 13C NMR were recorded with a spectrometer operating at 500 or 400
and 125 or 100 MHz for proton and carbon nuclei, respectively. IR spectra were obtained on an
FT−IR spectrometer, and samples were prepared by evaporation from CHCl3 on CsBr plates. High-
resolution mass spectra (HRMS) were obtained using positive electrospray ionization by the TOF
method.
General Procedure for Wacker-type Oxidation of Terminal Olefins to Methyl Ketones. To a
stirred solution of olefin (0.5 mmol, 1.0 equiv.) in CH3CN (3.5 mL) and H2O (0.5 mL) were added
Pd(OAc)2 (5.7 mg, 0.025 mmol, 5 mol%) and DMP (255 mg, 0.6 mmol, 1.2 equiv.) at room
temperature. The reaction mixture was warmed to 50 °C and stirred for a specified time under
nitrogen atmosphere. The reaction mixture was then filtered through a small pad of silica gel and
washed with EtOAc and the filtrate was concentrated. The residue was purified by silica gel column
chromatography using petroleum ether/EtOAc as eluent to afford the methyl ketones. Pd(OAc)2
(11.4 mg, 0.05 mmol, 10 mol%) and DMP (518 mg, 0.1.22 mmol, 2.4 equiv.) were used for terminal
olefins bearing two active olefin sites (compounds 1e, 1f, 5d and 5e).
Tetradecan-2-one (2a):17b Yield (101 mg, 95%). Colorless oil; IR (CHCl3): νmax = 3017, 2916, 1704,
1406, 1379, 1284,1165, 1131, 1018, 949, 717, 667 cm–1; H NMR (400 MHz, CDCl3/TMS): δ =
1
2.42 (t, J = 7.5 Hz, 2H), 2.14 (s, 3H), 1.58−1.55 (m, 4H), 1.36−1.19 (m, 16H), 0.88 (t, J = 6.8 Hz,
3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 209.3, 43.7, 31.8, 29.7, 29.6, 29.53, 29.5, 29.4, 29.3,
29.25, 29.1, 23.7, 22.6, 14.0.
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Octan-2-one (2b):17b Yield (47.4 mg, 74%). Colorless oil; H NMR (400 MHz, CDCl3/TMS): δ =
2.41 (t, J = 7.5 Hz, 2H), 2.13 (s, 3H), 1.59−1.52 (m, 2H), 1.32−1.21 (m, 6H), 0.87 (t, J = 6.9 Hz,
3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 209.5, 43.8, 31.6, 29.8, 28.8, 23.8, 22.5, 14.0.
Pentan-2-one (2c):20 Yield (31.0 mg, 72%). Colorless oil; IR (CHCl3): νmax = 2966, 2928, 1723,
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1385, 1259, 1034, 699,549 cm–1; H NMR (400 MHz, CDCl3/TMS): δ = 2.37 (t, J = 7.5 Hz, 2H),
2.09 (s, 3H), 1.59−1.52 (m, 2H), 0.87 (t, J = 6.9 Hz, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ =
209.4, 45.6, 29.8,17.2, 13.6.
Decan-2-one (2d):17b Yield (61.7 mg, 79%). Colorless oil; IR (CHCl3): νmax = 3020, 2950, 2928,
1715, 1465, 1401, 1361, 1163, 667 cm–1; 1H NMR (400 MHz, CDCl3/TMS): δ = 2.40 (t, J = 7.5 Hz,
2H), 2.11 (s, 3H), 1.55−1.52 (m, 2H), 1.30−1.22 (m, 10H), 0.86 (t, J = 6.9 Hz, 3H); 13C {1H} NMR
(100 MHz, CDCl3): δ = 209.4, 43.8, 31.8, 29.8, 29.3, 29.14, 29.1, 23.8, 22.6, 14.1. HRMS (ESI-
TOF) calcd for [C10H20O+Na]+ 179.1406, found 179.1409.
Decane-2,9-dione (2e):17b Yield (66.4 mg, 78%). Colorless oil; IR (CHCl3): νmax = 3019, 2933, 2858,
1717, 1409, 1363, 1168, 1048, 967, 927, 667 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 2.41 (t, J
= 7.4 Hz, 4H), 2.12 (s, 6H), 1.61−1.52 (m, 4H), 1.31−1.25 (m, 4H); 13C {1H} NMR (100 MHz,
CDCl3): δ = 209.2, 43.6, 29.9, 28.9, 23.5; HRMS (ESI-TOF) calcd for [C10H18O2+Na]+ 193.1199,
found 193.1198.
Dodecane-2,11-dione (2f):17b Yield (79.3 mg, 80%). Colorless oil; IR (CHCl3): νmax = 3017, 2916,
1704, 1406, 1379, 1284, 1165, 1131, 1018, 949, 717, 667 cm−1; 1H NMR (400 MHz, CDCl3/TMS):
δ = 2.40 (t, J = 7.4 Hz, 4H), 2.12 (s, 6H), 1.63−1.51 (m, 4H), 1.28−1.2 (m, 8H); 13C {1H} NMR (100
MHz, CDCl3): δ = 209.2, 43.6, 29.7, 29.1, 28.9, 23.6; HRMS (ESI-TOF) calcd for [C12H22O2+Na]+
221.1512, found 221.1512.
10-Bromodecan-2-one (2g):17b Yield (93 mg, 79%). Colorless oil; IR (CHCl3): νmax = 2927, 2850,
1715, 1466, 1361, 1220, 1163, 1037, 910, 726 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 3.39 (t,
J = 6.8 Hz, 2H), 2.41 (t, J = 7.4 Hz, 2H), 2.13 (s, 3H), 1.87−1.78 (m, 2H), 1.59−1.51 (m, 2H),
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1.42−1.38 (m, 2H), 1.29−1.23 (m, 6H); C {1H} NMR (100 MHz, CDCl3): δ = 209.3, 43.7, 34.0,
32.7, 29.8, 29.2, 29.0, 28.5, 28.0, 23.7; HRMS (ESI-TOF) calcd for [C10H19BrO+Na]+ 257.0511,
found 257.0511.
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13-Bromotridecan-2-one (2h):21 Yield (118.2 mg, 81%). Colorless oil; IR (CHCl3): νmax = 2927,
2850, 1715, 1466, 1361, 1220, 1163, 1037, 1024, 910, 736 cm−1; 1H NMR (400 MHz, CDCl3/TMS):
δ = 3.39 (t, J = 6.8 Hz, 2H), 2.41 (t, J = 7.4 Hz, 2H), 2.12 (s, 3H), 1.87−1.78 (m, 2H), 1.59−1.51 (m,
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2H), 1.42−1.38 (m, 2H), 1.29−1.23 (m, 12H); C {1H} NMR (100 MHz, CDCl3): δ = 209.5, 43.8,
34.0, 32.8, 29.8, 29.7, 29.4, 29.36, 29.1, 28.7, 28.1, 23.8; HRMS (ESI-TOF) calcd for
[C13H25BrO+Na]+ 299.0981, found 299.0977.
5-Oxohexyl benzoate (2i):17b Yield (85 mg, 77%). Colorless oil; IR (CHCl3): νmax = 2956, 2918,
2950, 1718, 1602, 1584, 1452, 1410, 1361, 1315, 1176, 1165, 1119, 1071, 1027, 963, 905, 807, 714,
1
688, 675 cm–1; H NMR (400 MHz, CDCl3/TMS): δ = 8.04−8.02 (m, 2H), 7.58− 7.53 (m, 1H),
7.46−7.40 (m, 2H), 4.36 (t, J = 6.1 Hz, 2H), 2.51 (t, J = 6.9 Hz, 2H), 2.15 (s, 3H), 1.82−1.70 (m,
13
4H); C {1H} NMR (100 MHz, CDCl3): δ = 208.5, 166.6, 132.9, 130.3, 129.5, 128.3, 64.5, 43.0,
29.9, 28.1, 20.2; HRMS (ESI-TOF) calcd for [C13H16O3+Na]+ 243.0992, found 243.0989.
11-(Methoxymethoxy)undecan-2-one (2j):17b Yield (75 mg, 65%). Colorless oil; IR (CHCl3): νmax
=
1
3014, 2929, 2856, 1716, 1465, 1410, 1361, 1145, 1111, 1043, 919, 667 cm−1; H NMR (400 MHz,
CDCl3/TMS): δ = 4.61 (s, 2H), 3.51 (t, J = 6.6 Hz, 2H), 3.35 (s, 3H), 2.41 (t, J = 7.5 Hz, 2H), 2.13
(s, 3H), 1.60−1.54 (m, 2H), 1.28−1.27 (m, 12H); 13C {1H} NMR (100 MHz, CDCl3): δ = 209.3, 96.3,
67.8, 55.0, 43.7, 29.8, 29.7, 29.3, 29.1, 26.1, 23.8; HRMS (ESITOF) calcd for [C13H26O3+Na]+
253.1774, found 253.1778.
1-(tert-Butyldiphenylsilyloxy)propan-2-one (2k):17b Yield (136 mg, 87%). Colorless oil; IR (CHCl3):
νmax = 3071, 3050, 2933, 2893, 2859, 1736, 1717, 1589, 1473, 1428, 1391, 1354, 1231, 1189, 1113,
1
940, 824, 703, 615 cm–1; H NMR (400 MHz, CDCl3/TMS): δ = 7.65 (dd, J = 7.2, 0.7 Hz, 4H),
13
7.44−7.38 (m, 6H), 4.16 (s, 2H), 2.20 (s, 3H), 1.10 (s, 9H); C {1H} NMR (100 MHz, CDCl3): δ =
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208.5, 135.5, 132.6, 130.0, 127.8, 69.9, 26.7, 26.3, 19.2; HRMS (ESI-TOF) calcd for
[C19H24O2Si+Na]+ 335.1438, found 335.1437.
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Ethyl 3-oxobutanoate (2l):17b Yield (57.3 mg, 88%). Colorless oil; 1H NMR (400 MHz,
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CDCl3/TMS): δ = 4.16 (q, J = 7.2 Hz, 2H), 3.40 (s, 2H), 2.23 (s, 3H), 1.25 (t, J = 7.1 Hz, 3H); C
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{1H} NMR (100 MHz, CDCl3): δ = 200.6, 167.1, 61.3, 50.1, 30.1, 14.0.
Methyl 10-oxo-undecanoate (2m):17a Yield (90 mg, 84%). Colorless oil; IR (CHCl3): νmax = 2931,
1
2857, 1740, 1717, 1459, 1437, 1362, 1197, 1171, 1103, 1017, 882, 669 cm1 ; H NMR (400 MHz,
CDCl3/TMS): δ = 3.65 (s, 3H), 2.40 (t, J = 7.4 Hz, 2H), 2.28 (t, J = 7.5 Hz, 2H), 2.12 (s, 3H), 1.61–
13
1.52 (m, 4H), 1.34−1.22 (m, 8H); C {1H} NMR (100 MHz, CDCl3): δ = 209.3, 174.3, 51.4, 43.7,
34.0, 29.8, 29.1, 29.03, 29.0, 24.9, 23.7; HRMS (ESI-TOF) calcd for [C12H22O3+Na]+ 237.1461,
found 237.1461.
10-Oxoundecanal (2n):22 Yield (73.7 mg, 80%). Colorless oil; IR (CHCl3): νmax = 2931, 2856, 2722,
1718, 1463, 1412, 1362, 1167, 1020, 758 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 9.71 (s, 1H),
2.40−2.35 (m, 4H), 2.09 (s, 3H), 1.61−1.48 (m, 4H), 1.31−1.18 (m, 8H); 13C {1H} NMR (100 MHz,
CDCl3): δ = 209.2, 202.8, 43.8, 43.6, 29.8, 29.0, 28.95, 23.7, 21.9; HRMS (ESI-TOF) calcd for
[C11H20O2+Na]+ 207.1356, found 207.1350.
4-Oxopentanoic Acid (2o):17b Yield (43.5 mg, 75%). Colorless oil; H NMR (400 MHz,
1
CDCl3/TMS): δ = 2.73 (t, J = 7.2 Hz, 2H), 2.61 (t, J = 7.2 Hz, 2H), 2.18 (s, 3H); 13C {1H} NMR (100
MHz, CDCl3): δ = 206.6, 178.2, 37.7, 29.8, 27.7.
5-Oxohexanoic Acid (2p):17a Yield (50.1 mg, 77%). Colorless oil; IR (CHCl3): νmax = 3501, 3020,
2920, 2851, 1715, 1416, 1373, 1161, 1070, 1049, 955, 668 cm–1; 1H NMR (400 MHz, CDCl3/TMS):
δ = 2.53 (t, J = 7.2 Hz, 2H), 2.39 (t, J = 7.2 Hz, 2H), 2.15 (s, 3H), 1.94−1.84 (m, 2H); 13C {1H} NMR
(100 MHz, CDCl3): δ = 208.0, 178.7, 42.3, 32.8, 29.9, 18.5. HRMS (ESI-TOF) calcd for
[C6H10O3+Na]+ 153.0522,found 153.0525.
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16-Hydroxyheptadecane-2-one (2r):17b Yield (75.7 mg, 56%). White solid; mp 55−57 °C; IR
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(CHCl3): νmax = 3402, 2916, 2849, 1709, 1464, 1372, 1163, 1124, 1038, 910, 667 cm−1; H NMR
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(500 MHz, CDCl3/TMS): δ = 3.78−3.75 (m, 1H), 2.38 (t, J = 7.4 Hz, 2H), 2.10 (s, 3H), 1.55−1.51
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(m, 2H), 1.39−1.38 (m, 2H), 1.35−1.22 (m, 20H), 1.15 (d,J = 6.2 Hz, 3H); C {1H} NMR (100
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MHz, CDCl3): δ = 209.4, 68.1, 43.8, 39.3, 29.8, 29.6, 29.59, 29.56, 29.5, 29.4, 29.3, 29.1, 25.7, 23.8,
23.4; HRMS (ESI-TOF) calcd for [C17H34O2+Na]+ 293.2451,found 293.2455.
Acetophenone (4a):17b Yield (51.7 mg, 86%). Pale yellow oil; 1H NMR (400 MHz, CDCl3/TMS): δ =
7.98−7.92 (m, 2H), 7.60−7.51 (m, 1H), 7.50−7.42 (m, 2H), 2.60 (s, 3H).13C {1H} NMR (100 MHz,
CDCl3): δ = 198.1, 137.0, 133.0, 128.5, 128.2, 26.5.
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4-Methoxyacetophenone (4b):17b Yield (63.8 mg, 85%). Colorless oil; H NMR (400 MHz,
CDCl3/TMS): δ = 7.94 (d, J = 8.6 Hz, 2H), 6.94 (d, J= 8.6 Hz, 2H), 3.87 (s, 3H), 2.56 (s, 3H).
4-Methylacetophenone (4c):17a Yield (55.7 mg, 83%). Colorless oil; IR (CHCl3): νmax = 3032, 3005,
2961, 2924, 2857, 1682, 1607, 1569, 1429, 1407, 1358, 1269, 1182, 1019, 954, 912, 815, 734 cm-1 ;
1H NMR (400 MHz, CDCl3/TMS): δ = 7.86 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 8.0 Hz, 2H), 2.58 (s,
13
3H), 2.41 (s, 3H); C {1H} NMR (100 MHz, CDCl3): δ = 197.9, 143.9, 134.7, 129.2, 128.4, 26.5,
21.6; HRMS (ESI-TOF) calcd for [C9H10O+Na]+ 157.0624, found 157.0623.
2,5-Dimethoxyacetophenone (4d):17b Yield (76.6 mg, 85%). Colorless oil; IR (CHCl3): νmax = 3014,
1
2929, 2856, 1716, 1465, 1410, 1361, 1145, 1111, 1043, 919, 667 cm−1; H NMR (400 MHz,
CDCl3/TMS): δ = 7.28 (d, J = 3.2 Hz, 1H), 7.02 (dd, J = 8.6, 3.6 Hz, 1H), 6.90 (d, J = 9.0 Hz, 1H),
3.87 (s, 3H), 3.78 (s, 3H), 2.61 (s, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 199.4, 153.5, 153.4,
128.3, 120.4, 113.8, 113.2, 56.0, 55.8, 31.8; HRMS (ESI-TOF) calcd for [C10H12O3+Na]+ 203.0679,
found 203.0682.
3,4-Dimethoxyacetophenone (4e):17a Yield (78.4 mg, 87%); Colorless oil; IR (CHCl3) νmax = 3080,
3005, 2962, 2938, 2840, 1673, 1588, 1513, 1463, 1417, 1358, 1334, 1270, 1224, 1175, 1150, 1135,
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1079, 1023, 976, 915, 878, 808, 732, 645 cm-1; 1H NMR (400 MHz, CDCl3/TMS): δ = 7.58 (dd, J =
8.4, 2.0 Hz, 1H), 7.55 (d, J = 2.0 Hz, 1H), 6.89 (d, J = 8.4 Hz, 1H), 3.95 (s, 3H), 3.94 (s, 3H), 2.57
(s, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 196.7, 153.1, 148.8, 130.3, 123.2, 109.9, 109.8, 55.9,
55.8, 26.1; HRMS (ESI-TOF) calcd for [C10H12O3+H] + 181.0859, found 181.0862.
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4-tert-Butylacetophenone (4f):17b Yield (65.2 mg, 74%). Colorless oil; IR (CHCl3): νmax = 2965,
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2907, 2871, 1719, 1685, 1607, 1407, 1363, 1271, 1114, 1015, 958, 838, 777, 701 cm−1; H NMR
(400 MHz, CDCl3/TMS): δ = 7.90 (d, J = 8.7 Hz, 2H), 7.48 (d, J = 8.7 Hz, 2H), 2.58 (s, 3H), 1.34 (s,
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9H); C {1H} NMR (100 MHz, CDCl3): δ = 197.9, 156.8, 134.5, 128.3, 125.5, 35.1, 31.0, 26.5;
HRMS (ESI-TOF) calcd for [C12H16O+H]+ 177.1274, found 177.1276.
4-Nitroacetophenone (4g):17b Yield (53.7 mg, 65%). Pale yellow solid; mp 76−78 °C; 1H NMR (400
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MHz, CDCl3/TMS): δ = 8.32 (d, J = 8.8 Hz, 2H), 8.11 (d, J = 8.8 Hz, 2H), 2.68 (s, 3H); C {1H}
NMR (100 MHz, CDCl3): δ = 196.3, 150.7, 141.6, 129.3, 123.9, 27.0.
4-Phenylacetophenone (4h):17b Yield (70.6 mg, 72%). White solid; mp 115−117 °C; IR (CHCl3):
νmax = 3019, 2923, 1679, 1599, 1404, 1359, 1267, 1119, 1078, 1044, 957, 927, 842, 694, 669 cm−1;
1H NMR (400 MHz, CDCl3/TMS): δ = 8.04 (d, J = 8.6 Hz, 2H), 7.69 (d, J = 8.6 Hz, 2H), 7.63 (d, J
= 7.0 Hz, 2H), 7.50−7.41 (m, 3H), 2.65 (s, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 197.8, 145.8,
139.9, 135.8, 128.94, 128.9, 128.2, 127.3, 127.2, 26.6; HRMS (ESI-TOF) calcd for [C14H12O+Na]+
219.0780, found 219.0783.
2-Acetylnapthalene (4i):17b Yield (52 mg, 61%). Colorless oil; 1H NMR (400 MHz, CDCl3/TMS): δ
= 8.48 (s, 1H), 8.04 (dd, J = 8.7, 1.7 Hz, 1H), 7.97 (d, J = 8.2 Hz, 1H), 7.92−7.86 (m, 2H), 7.66−
7.53 (m, 2H), 2.73 (s, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 198.2, 135.6, 134.5, 132.5, 130.2,
129.5, 128.6, 128.5, 127.8, 126.8, 123.9, 26.7.
4-Chloroacetophenone (4j):17a Yield (60.3 mg, 78%). Colorless oil; IR (CHCl3): νmax =3018, 2927,
1
2855, 1687, 1590, 1572, 1488, 1429, 1397, 1358, 1261, 1095, 1013, 958, 831, 668 cm−1; H NMR
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(400 MHz, CDCl3/TMS) δ = 7.89 (d, J = 8.6 Hz, 2H), 7.43 (d, J = 8.7 Hz, 2H), 2.58 (s, 3H); C
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{1H} NMR (100 MHz, CDCl3): δ = 196.8, 139.5, 135.4, 129.7, 128.9, 26.5.
2-Acetylpyridine (4k):23 Yield (46 mg, 76%). Colorless oil; IR (CHCl3): νmax = 3010, 1700, 1584,
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1437, 1358, 1283, 1239, 1101, 1044, 955, 591 cm−1; H NMR (400 MHz, CDCl3/TMS): δ =
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8.68−8.66 (m, 1H), 8.04−8.02 (m, 1H), 7.83−7.78 (m, 1H), 7.48−7.43 (m, 1H), 2.72 (s, 3H); 13C
{1H} NMR (100 MHz, CDCl3): δ = 200.0, 153.5, 148.9, 136.8, 127.0, 121.6, 25.7.
4-Acetylpyridine (4l):24 Yield (46 mg, 76%). Colorless oil; IR (CHCl3): νmax = 3048, 1697, 1557,
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1409, 1363, 1267, 1221, 1063, 1020, 992, 962, 818, 600, 588 cm−1; H NMR (400 MHz,
CDCl3/TMS): δ = 8.76 (d, J = 8.4 Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H), 2.52 (s, 3H); 13C {1H} NMR
(100 MHz, CDCl3): δ = 197.1, 150.7, 142.7, 121.2, 26.5.
2-Acetylthiophene (4m):25 Yield (47.3 mg, 75%). Brown oil; IR (CHCl3): νmax = 3091, 1663, 1518,
1415, 1357, 1275, 1035, 934, 858, 676, 592 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 7.69 (dd, J
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= 5.0, 1.4 Hz, 1H), 7.63 (dd, J = 3.5, 1.4 Hz, 1H), 7.12 (dd, J = 5.0, 3.5 Hz, 1H), 2.56 (s, 3H). C
{1H} NMR (100 MHz, CDCl3): δ = 190.7, 144.5, 133.7, 132.4, 128.1. 26.8.
2-(2-Oxopropoxy)benzoic Acid (6c):17b Yield (74.8 mg, 77%). Colorless oil; IR (CHCl3): νmax
=
3212, 2919, 1781, 1717, 1600, 1485, 1458, 1418, 1341, 1295, 1252, 1184, 1165, 1095, 1058, 1036,
958, 862, 829, 684, 646 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 8.18 (dd, J = 7.8, 1.4 Hz, 1H),
7.53 (t, J = 7.2 Hz, 1H), 7.18 (t, J = 7.6 Hz, 1H), 6.91 (d, J = 8.2 Hz, 1H), 4.89 (s, 2H), 2.30 (s, 3H);
13C {1H} NMR (100 MHz, CDCl3): δ = 201.2, 165.4, 156.3, 134.8, 134.1, 123.0, 118.9, 113.0, 73.7,
26.1; HRMS (ESI-TOF) calcd for [C10H10O4+Na]+ 217.0471, found 217.0472.
2-Oxopropyl 2-(2-oxopropoxy)benzoate (6d):17b Yield (96.3 mg, 77%). White solid; mp 62−64 °C;
IR (CHCl3): νmax = 3020, 2928, 2846, 1728, 1603, 1586, 1491, 1457, 1420, 1364, 1306, 1253, 1180,
1168, 1134, 1097, 1060, 1012, 964, 884, 828, 703, 668 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ =
7.96 (dd, J = 7.8, 1.8 Hz, 1H), 7.51−7.48 (m, 1H), 7.1 (td, J = 7.6, 0.8 Hz, 1H), 6.84 (d, J = 8.3 Hz,
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1H), 4.88 (s, 2H), 4.60 (s, 2H), 2.35 (s, 3H), 2.23 (s, 3H); C {1H} NMR (100 MHz, CDCl3): δ =
205.7, 201.7, 164.7, 157.6, 134.3, 132.4, 121.5, 119.5, 113.6, 73.9, 68.6, 26.9, 26.2; HRMS (ESI-
TOF) calcd for [C13H14O5+Na]+ 273.0733, found 273.0700.
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2-Oxopropyl 4-(2-oxopropoxy)benzoate (6e):17b Yield (95.1 mg, 76%). White solid; mp 80−82 °C;
IR (CHCl3): νmax = 3021, 2928, 1721, 1607, 1583, 1509, 1420, 1371, 1314, 1276, 1170, 1115, 1070,
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1008, 966, 883, 848, 696, 667 cm−1; H NMR (400 MHz, CDCl3/ TMS): δ = 8.03 (d, J = 9.0 Hz,
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2H), 6.91 (d, J = 9.0 Hz, 2H), 4.82 (s, 2H), 4.61 (s, 2H), 2.28 (s, 3H), 2.21 (s, 3H); C {1H} NMR
(100 MHz, CDCl3): δ = 204.3, 201.9, 165.3, 161.7, 132.1, 122.6, 114.3, 72.8, 68.6, 26.5, 26.2;
HRMS (ESI-TOF) calcd for [C13H14O5+Na]+ 273.0733, found 273.0734.
1-Phenoxypropan-2-one (6f):17b Yield (63.1 mg, 84%). Colorless oil; IR (CHCl3): νmax = 3043, 3065,
2919, 2849, 1733, 1599, 1590, 1496, 1457, 1433, 1359, 1305, 1295, 1228, 1172, 1155,1085, 1067,
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967, 888, 817, 806, 782, 692 cm−1; H NMR (400 MHz, CDCl3/TMS): δ = 7.33−7.28 (m, 2H),
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7.02−6.98 (m, 1H), 6.91−6.88 (m, 2H), 4.54 (s, 2H), 2.28 (s, 3H); C {1H} NMR (100 MHz,
CDCl3): δ = 205.9, 157.6, 129.6, 121.7, 114.4, 72.9, 26.6; HRMS (ESI-TOF) calcd for
[C9H10O2+Na]+ 173.0573, found 173.0573.
1-(Benzyloxy)propan-2-one (6g):17b Yield (68.1 mg, 83%). Colorless oil; IR (CHCl3): νmax = 3067,
3032, 2868, 1729, 1603, 1584, 1497, 1455, 1376, 1357, 1276, 1226, 1167, 1118, 1074, 1028, 1013,
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939, 868, 699, 682 cm−1; H NMR (400 MHz, CDCl3/TMS): δ = 7.38−7.25 (m, 5H), 4.58 (s, 2H),
4.07 (s, 2H), 2.16 (s, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 206.6, 137.1, 128.5, 128.0, 127.8,
75.2, 73.3, 26.4; HRMS (ESI-TOF) calcd for [C10H12O2+Na]+ 187.0730, found 187.0729.
1-[4-(tert-Butyl)phenoxy]propan-2-one (6h):17b Yield (77.4 mg, 75%). Colorless oil; IR (CHCl3):
νmax = 3041, 2963, 2906, 2869, 1724, 1610, 1583, 1514, 1480, 1464, 1435, 1364, 1297, 1255, 1234,
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1185, 1066, 829, 809, 682 cm−1; H NMR (400 MHz, CDCl3/TMS): δ = 7.32 (d, J = 8.9 Hz, 2H),
6.82 (d, J = 8.9 Hz, 2H), 4.52 (s, 2H), 2.28 (s, 3H), 1.30 (s, 9H); 13C {1H} NMR (100 MHz, CDCl3):
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δ = 206.4, 155.5, 144.5, 126.5, 114.0, 73.2, 34.1, 31.5, 26.6; HRMS (ESI-TOF) calcd for
[C13H18O2+Na]+ 229.1199, found 229.1199.
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1-(Napthalen-2-yloxy)propan-2-one (6i):17b Yield (76.1 mg, 76%). White solid; mp 64−66 °C; IR
(CHCl3): νmax = 3028, 3056, 2924, 2850, 1732, 1631, 1600, 1509, 1470, 1432, 1390, 1358, 1272,
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1259, 1222, 1173, 1122, 1071, 978, 950, 908, 875, 838, 819, 638 cm−1; H NMR (400 MHz,
CDCl3/TMS): δ = 7.79 (d, J = 8.8 Hz, 2H), 7.72 (d, J = 8.2 Hz, 1H), 7.48−7.44 (m, 1H), 7.39−7.35
(m, 1H), 7.22 (dd, J = 9.0, 2.6 Hz, 1H), 7.03 (d, J = 2.5 Hz, 1H), 4.66 (s, 2H), 2.33 (s, 3H); 13C {1H}
NMR (100 MHz, CDCl3): δ = 205.9, 155.6, 134.2, 129.9, 129.3, 127.7, 126.8, 126.6, 124.2, 118.5,
106.9, 73.0, 26.7; HRMS (ESI-TOF) calcd for [C13H12O2+Na]+ 223.0730, found 223.0729.
1-(2-Bromo-5-methoxyphenoxy)propan-2-one (6j):17a Yield (105 mg, 81%). White solid; mp 68–70
°C; IR (CHCl3): νmax = 2939, 1721, 1586, 1488, 1462, 1432, 1359, 1307, 1283, 1263, 1201, 1169,
1067, 1024, 910, 832, 649 cm−1; H NMR (400 MHz, CDCl3/TMS): δ = 7.45 (d, J = 8.7 Hz, 1H),
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6.46 (dd, J = 8.7, 2.7 Hz, 1H), 6.35 (d, J = 2.7 Hz, 1H), 4.52 (s, 2H), 3.78 (s, 3H), 2.38 (s, 3H); 13C
{1H} NMR (100 MHz, CDCl3): δ = 205.6, 160.1, 154.7, 133.5, 107.1, 102.7, 101.0, 73.6, 55.6, 27.0;
HRMS (ESI-TOF) calcd for [C10H11BrO3+Na]+ 280.9784, found 280.9783.
2-Oxopropyl 4-methylbenzoate (6k):17b Yield (83.6 mg, 87%). Colorless oil; IR (CHCl3): νmax
=
3036, 3006, 2927, 1735, 1719, 1611, 1577, 1509, 1420, 1374, 1279, 1177, 1112, 1022, 962, 841,
691, 639 cm−1; H NMR (400 MHz, CDCl3/TMS): δ = 7.97 (d, J = 8.2 Hz, 2H), 7.26 (d, J = 8.1 Hz,
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2H), 4.86 (s, 2H), 2.40 (s, 3H), 2.22 (s, 3H); C {1H} NMR (100 MHz, CDCl3): δ = 202.1, 165.9,
144.2, 129.9, 129.2, 126.3, 68.6, 26.2, 21.6; HRMS (ESI-TOF) calcd for [C11H12O3+Na]+ 215.0679,
found 215.0675.
2-Oxopropyl 4-nitrobenzoate (6l):17b Yield (71.4 mg, 64%). White solid; mp 102−104 °C; IR
(CHCl3): νmax = 3115, 3081, 3060, 2977, 2934, 2855, 1742, 1721, 1607, 1524, 1421, 1367, 1320,
1274, 1184, 1120, 1106, 1011, 964, 883, 855, 720, 623 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ =
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8.28 (d, J = 9.1 Hz, 2H), 8.23 (d, J = 9.1 Hz, 2H), 4.97 (s, 2H), 2.23 (s, 3H); C {1H} NMR (100
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MHz, CDCl3): δ = 200.3, 164.0, 150.7, 134.6, 131.0, 123.6, 69.1, 26.1; HRMS (ESI-TOF) calcd for
[C10H9O5N+Na]+ 246.0373, found 246.0379.
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2-Oxopropyl 3,5-dinitrobenzoate (6m):17b Yield (84.5 mg, 63%). White solid; mp 139−141 °C; IR
(CHCl3): νmax = 3093, 3020, 2923, 1735, 1630, 1599, 1547, 1462, 1418, 1345, 1285, 1157, 1075,
1035, 923, 905, 669 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 9.27− 9.25 (m, 1H), 9.24−9.20 (m,
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2H), 5.05 (s, 2H), 2.27 (s, 3H); C {1H} NMR (100 MHz, CDCl3): δ = 199.1, 161.9, 148.7, 132.9,
129.7, 122.8, 69.6, 25.9; HRMS (ESI-TOF) calcd for [C10H8O7N2+Na]+ 291.0224, found 291.0230.
3-Oxo-1-phenylbutyl acetate (6n):17b Yield (75.3 mg, 73%). Colorless oil; IR (CHCl3): νmax = 3064,
3032, 2927, 2853, 1736, 1721, 1608, 1495, 1454, 1373, 1239, 1163, 1043, 950, 917, 871, 701, 667
cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 7.37−7.28 (m, 5H), 6.18 (dd, J = 8.7, 4.9 Hz, 1H), 3.12
(dd, J = 16.6, 8.7 Hz, 1H), 2.82 (dd, J = 16.7, 4.9 Hz, 1H), 2.15 (s, 3H), 2.04 (s, 3H); 13C {1H} NMR
(100 MHz, CDCl3): δ = 204.7, 169.8, 139.6, 128.6, 128.2, 126.4, 71.6, 49.8, 30.4, 21.0; HRMS (ESI-
TOF) calcd for [C12H14O3+Na]+ 229.0835, found 229.0835.
1-(Benzo[d][1,3]dioxol-5-yl)-3-oxobutyl acetate (6o):17a Yield (101.4 mg, 81%). Colorless oil; IR
(CHCl3): νmax = 2919, 2852, 1773, 1736, 1660, 1625, 1600, 1503, 1489, 1448, 1359, 1239, 1178,
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1103, 1037, 977, 929, 804, 788 cm−1; H NMR (400 MHz, CDCl3/ TMS): δ = 6.84–6.75 (m, 3H),
6.09 (dd, J = 8.5, 5.1 Hz, 1H), 5.94 (s, 2H), 3.27 (dd, J = 16.6, 8.5 Hz, 1H), 2.80 (dd, J = 16.6, 5.2
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Hz, 1H), 2.14 (s, 3H), 2.02 (s, 3H); C {1H} NMR (100 MHz, CDCl3): δ = 204.7, 169.8, 147.8,
147.5, 133.4, 120.3, 108.3, 106.9, 101.1, 71.4, 49.8, 30.4, 21.1; HRMS (ESI-TOF) calcd for
[C13H14O5+Na] + 273.0733, found 273.0735.
1-(4-Methoxyphenyl)-3-oxobutyl acetate (6p):17b Yield (89.8 mg, 76%). Colorless oil; IR (CHCl3):
νmax = 3003, 2960, 2936, 2840, 1740, 1729, 1612, 1516, 1464, 1424, 1372, 1303, 1177, 1033, 948,
835, 657 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 7.29 (d, J = 8.7 Hz, 2H), 6.86 (d, J = 8.7 Hz,
2H), 6.13 (dd, J = 8.5, 5.3 Hz, 1H), 3.78 (s, 3H), 3.10 (dd, J = 16.5, 8.5 Hz, 1H), 2.81 (dd, J = 16.5,
5.3 Hz, 1H), 2.14 (s, 3H), 2.01 (s, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 204.8, 169.9, 159.5,
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131.6, 128.0, 113.9, 71.3, 55.2, 49.6, 30.4, 21.1; HRMS (ESI-TOF) calcd for [C13H16O4+Na]+
259.0941, found 259.0948.
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1-(Naphthalen-1-yl)-3-oxobutyl benzoate (6q):17b Yield (127.4 mg, 80%). Colorless oil; IR (CHCl3):
νmax = 3062, 3009, 2925, 2854, 1719, 1601, 1584, 1510, 1492, 1451, 1417, 1398, 1363, 1315, 1270,
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1176, 1110, 1070, 1058, 1026, 975, 938, 862, 798, 713, 686 cm−1; H NMR (400 MHz,
CDCl3/TMS): δ = 8.25 (d, J = 8.4 Hz, 1H), 8.10−8.07 (m, 2H), 7.88 (d, J = 7.6 Hz, 1H), 7.80 (d, J =
8.2 Hz, 1H), 7.64−7.42 (m, 7H), 7.21 (dd, J = 9.0, 4.0 Hz, 1H), 3.40 (dd, J = 16.9, 8.6 Hz, 1H), 3.13
(dd, J = 16.9, 4.1 Hz, 1H), 2.23 (s, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 204.6, 165.3, 135.6,
133.9, 133.1, 129.9, 129.8, 129.6, 129.0, 128.9, 128.7, 126.6, 125.8, 125.3, 123.7, 122.9, 69.9, 49.6,
30.4; HRMS (ESI-TOF) calcd for [C21H18O3+Na]+ 341.1148, found 341.1148.
4-(Benzyloxy)-4-(4-nitrophenyl)butan-2-one (6r):17b Yield (82.3 mg, 55%). Colorless oil; IR
(CHCl3): νmax = 3066, 3032, 3008, 2865, 1716, 1606, 1521, 1497, 1415, 1347, 1162, 1096, 1075,
1028, 884, 857, 699 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 8.15 (d, J = 8.8 Hz, 2H), 7.48 (d, J
= 8.7 Hz, 2H), 7.27−7.21 (m, 5H), 4.93 (dd, J = 8.4, 4.6 Hz, 1H), 4.32 (d, J = 11.3 Hz, 1H), 4.27 (d,
J = 11.3 Hz, 1H), 2.99 (dd, J = 16.5, 8.5 Hz, 1H), 2.57 (dd, J = 16.5, 4.6 Hz, 1H), 2.10 (s, 3H); 13C
{1H} NMR (100 MHz, CDCl3): δ = 205.3, 148.9, 147.6, 137.2, 128.4, 127.9, 127.9, 127.5, 123.9,
76.5, 71.5, 51.5, 31.0; HRMS (ESI-TOF) calcd for [C17H17NO4+Na]+ 322.1050, found 322.1049.
2-Oxononan-4-yl Acetate (6s):17b Yield (77.1 mg, 77%). Colorless oil; IR (CHCl3): νmax = 3011,
2950, 2932, 2861, 1736, 1717, 1677, 1628, 1459, 1424, 1364, 1248, 1166, 1023, 981, 960, 667 cm−1;
1H NMR (400 MHz, CDCl3/TMS): δ = 5.22−5.16 (m, 1H), 2.70 (dd, J = 16.2, 7.4 Hz, 1H), 2.57 (dd,
J = 16.2, 5.3 Hz, 1H), 2.13 (s, 3H), 2.01 (s, 3H), 1.54−1.51 (m, 2H), 1.32−1.21 (m, 6H), 0.86 (t, J =
6.8 Hz, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 205.8, 170.5, 70.3, 48.0, 34.1, 31.5, 30.4, 24.8,
22.5, 21.1, 14.0. HRMS (ESI-TOF) calcd for [C11H20O3+Na]+ 223.1305, found 223.1307.
4-(tert-Butyldiphenylsilyloxy)-4-phenylbutan-2-one (6t):17a Yield (159 mg, 79%). Colorless oil; IR
(CHCl3): νmax = 3070, 2999, 2931, 2894, 2858, 1716, 1589, 1472, 1454, 1427, 1391, 1361, 1309,
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1259, 1190, 1161, 1111, 1028, 1007, 956, 912, 855, 822, 701, 613 cm−1; H NMR (400 MHz,
CDCl3/ TMS): δ = 7.65−7.63 (m, 2H), 7.44–7.40 (m, 3H), 7.38–7.32 (m, 3H), 7.25–7.18 (m, 7H),
5.15 (t, J = 6.5 Hz, 1H), 2.92 (dd, J = 15.2, 6.5 Hz, 1H), 2.71 (dd, J = 15.2, 6.4 Hz, 1H), 1.90 (s, 3H),
1.01 (s, 9H); 13C {1H} NMR (100 MHz, CDCl3): δ = 206.4, 143.5, 135.8, 133.7, 133.2, 129.7, 129.5,
128.1, 127.5, 127.4, 127.3, 126.2, 72.3, 54.1, 31.1, 26.9, 19.2; HRMS (ESI-TOF) calcd for
[C26H30O2Si+Na]+ 425.1907, found 425.1904.
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1-(tert-Butyldiphenylsilyloxy)-1-phenylpropan-2-one (6u):17b Yield (149.6 mg, 77%). Colorless oil;
IR (CHCl3): νmax = 3070, 2961, 2932, 2894, 2859, 1717, 1589, 1492, 1472, 1428, 1391, 1351, 1307,
1190, 1113, 1070, 1028, 910, 855, 823, 701, 648 cm−1; H NMR (400 MHz, CDCl3/ TMS): δ =
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7.66−7.64 (m, 2H), 7.47−7.42 (m, 3H), 7.40−7.32 (m, 5H), 7.31−7.27 (m, 5H), 5.08 (s, 1H), 2.02 (s,
3H), 1.13 (m, 9H); 13C {1H} NMR (100 MHz, CDCl3): δ = 207.7, 138.2, 135.7, 135.6, 132.8, 132.6,
130.0, 129.8, 128.5, 128.1, 127.8, 127.6, 126.2, 81.7, 26.9, 24.3, 19.3; HRMS (ESI-TOF) calcd for
[C25H28O2Si + Na]+ 411.1751, found 411.1755.
2-Oxononan-3-yl acetate (6v):17b Yield (82.1 mg, 82%). Colorless oil; IR (CHCl3): νmax = 3027,
2956, 2929, 2851, 1744, 1731, 1462, 1429, 1376, 1239, 1122, 1072, 1046, 668 cm−1; 1H NMR (400
MHz, CDCl3/TMS): δ = 4.98 (dd, J = 8.2, 4.6 Hz, 1H), 2.16 (s, 3H), 2.15 (s, 3H), 1.76−1.71 (m,
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2H), 1.54−1.25 (m, 8H), 0.88 (t, J = 6.8 Hz, 3H); C {1H} NMR (100 MHz, CDCl3): δ = 205.5,
170.7, 78.7, 31.5, 30.2, 28.9, 26.1, 25.1, 22.5, 20.7, 14.0.
3-(Methoxymethoxy)nonan-2-one (6w):17a Yield (80.9 mg, 80%). Colorless oil; IR (CHCl3): νmax
=
3019, 2956, 2928, 2857, 1719, 1466, 1355, 1153, 1122, 1104, 1037, 921, 669 cm−1; H NMR (400
MHz, CDCl3/TMS): δ = 4.64 (s, 2H), 3.97 (t, J = 6.3 Hz, 1H), 3.38 (s, 3H), 2.17 (s, 3H), 1.66–1.62
(m, 2H), 1.41–1.32 (m, 8H), 0.87 (t, J = 6.8 Hz, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 210.1,
96.4, 82.8, 56.0, 32.0, 31.6, 29.0, 25.9, 25.1, 22.5, 14.0; HRMS (ESI-TOF) calcd for
[C11H22O3+Na]+ 225.1461, found 225.1459.
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2-Oxo-1-phenylpropyl Acetate (6x):17b Yield (70.1 mg, 73%). Colorless oil; IR (CHCl3): νmax = 3065,
3030, 2925, 2854, 1745, 1733, 1678, 1626, 1603, 1496, 1455, 1428, 1373, 1234, 1169, 1124, 1081,
1051, 961, 941, 914, 866, 700 cm−1; 1H NMR (400 MHz, CDCl3/TMS): δ = 7.44−7.38 (m, 5H), 5.97
(s, 1H), 2.20 (s, 3H), 2.12 (s, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ = 201.7, 170.3, 133.1, 129.4,
129.1, 128.1, 80.9, 26.1, 20.7; HRMS (ESI-TOF) calcd for[C11H12O3+Na]+ 215.0679, found
215.0676.
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2-Oxopentan-3-yl 2-(3-fluorophenyl)acetate (6y): Yield (90.5mg, 76%). Colorless oil; IR (CHCl3):
νmax = 2921, 2850, 1742, 1731,1613, 1593, 1490, 1452, 1265, 1144, 1114 cm−1; 1H NMR (400 MHz,
CDCl3/TMS): δ = 7.31−7.27 (m, 1H), 7.11−6.95 (m, 3H), 4.96 (dd, J = 7.8, 4.6 Hz, 1H), 3.71 (s,
2H), 2.09 (s, 3H), 1.83−1.72 (m, 2H), 0.93 (t, J = 7.4 Hz, 3H); 13C {1H} NMR (100 MHz, CDCl3): δ
= 204.8, 170.6, 164.02 and 161.58 (JC,F = 244 Hz), 135.81 and 135.74 (JC,F = 7.0 Hz), 130.08 and
130.0 (JC,F = 8.0 Hz), 125.04 and 125.01 (JC,F = 3.0 Hz), 116.49 and 116.27 (JC,F =22.0 Hz), 114.35
and 114.14 (JC,F = 21.0 Hz), 80.15, 40.68 and 40.67 (JC,F = 1.0 Hz), 26.2, 23.6, 9.4 ppm; HRMS
(ESI-TOF) calcd for [C13H15FO3+Na]+ 261.0897 found 261.0902.
1-[(1R,2S,5R)-2-Isopropyl-5-methylcyclohexyloxy]propan-2-one (6aa):17b Yield (55.2 mg, 52%).
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Colorless oil; [α]D = −73.3 (c = 1.0, CHCl3); IR (CHCl3): νmax = 3020, 2958, 2928, 2872, 1720,
1
1457, 1370, 1116, 1015, 938, 842, 668 cm−1; H NMR (400 MHz, CDCl3/ TMS): δ = 4.14 (d, J =
16.8 Hz, 1H), 3.93 (d, J = 16.8 Hz, 1H), 3.11 (td, J = 10.6, 4.1 Hz, 1H), 2.28−2.24 (m, 1H), 2.18 (s,
3H), 2.06−2.00 (m, 1H), 1.68−1.61 (m, 2H), 1.37−1.28 (m, 2H), 1.01−0.84 (m, 8H), 0.78 (d, J = 7.0
Hz, 4H); 13C {1H} NMR (125 MHz, CDCl3): δ = 208.0, 80.3, 74.3, 48.0, 40.0, 34.4, 31.4, 26.6, 25.6,
23.2, 22.2, 20.9, 16.1; HRMS (ESI-TOF) calcd for [C13H24O2 + Na]+ 235.1669, found 235.1666.
Methyl 3-acetyloctanoate (6ab):26 Yield (66.1 mg, 66%). Colorless oil; IR (CHCl3): νmax = 2959,
1
2931, 2864, 1740, 1718, 1459, 1439, 1356, 1205, 1165, 1068, 1021, 898, 600 cm−1; H NMR (400
MHz, CDCl3/TMS): δ = 3.58 (s, 3H), 3.01–2.94 (m, 1H), 2.78−2.69 (m, 1H), 2.38−2.29 (m, 1H),
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2.22 (s, 3H), 1.59–1.50 (m, 1H), 1.39–1.21 (m, 7H), 0.87 (t, J = 6.1 Hz, 3H); C {1H} NMR (100
MHz, CDCl3): δ = 210.9, 173.0, 51.7, 47.9, 35.0, 31.7, 31.3, 29.5, 26.5, 22.4, 13.9; HRMS (ESI-
TOF) calcd for [C11H20O3+Na]+ 223.1306, found 223.1305.
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Methyl 3-(4-nitrophenyl)-4-oxopentanoate (6ac): Yield (82.9 mg, 66%). Light yellow solid; mp
10
11
12
13
14
15
16
17
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1
108−110 °C; IR (CHCl3): νmax = 3020, 1720, 1525, 1349, 1216, 1018, 669 cm−1; H NMR (400
MHz, CDCl3/TMS): δ = 8.21 (dd, J = 6.8, 2.0 Hz, 2H), 7.42 (dd, J = 6.8, 2.0 Hz, 2H), 4.34–4.30 (m,
13
1H), 3.6 (s, 3H), 3.27–3.20 (m, 1H), 2.57 (dd, J = 17.0, 5.4 Hz, 1H), 2.15 (s, 3H); C {1H} NMR
(100 MHz, CDCl3): δ = 205.2, 171.8, 144.52, 129.2, 124.8, 54.4, 52.0, 36.6, 29.7; HRMS (ESI-TOF)
calcd for [C12H13NO5+Na]+ 274.0686, found 274.0686.
2-(2-Oxopropyl)isoindoline-1,3-dione (6ad):27 Yield (80.3 mg, 79%). White solid; mp 110−112 °C;
1
IR (CHCl3): νmax = 2925, 1771, 1724, 1416, 1369, 1307, 1190, 1018, 725, 714 cm−1; H NMR (400
MHz, CDCl3/TMS): δ = 7.85 (dd, J= 5.4, 2.7 Hz, 2H), 7.72 (dd, J= 5.4, 2.7 Hz, 2H), 4.48 (s, 2H),
13
2.25 (s, 3H); C {1H} NMR (100 MHz, CDCl3): δ = 199.7, 167.6, 134.1, 131.9, 123.4, 47.0, 26.9;
HRMS (ESI-TOF) calcd for [C11H9NO3+Na]+ 226.0475, found 226.0474.
ASSOCIATED CONTENT
Acknowledgements
This activity was supported by the Council of Scientific and Industrial Research (CSIR) New Delhi
[Grant No. 02 (0158)/13/EMR-II], India. Financial support received from CSIR-India (fellowship to
D.A.C) is gratefully acknowledged.
Supporting Information
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Copies of H and C NMR spectra for all compounds. This material is available free of charge via
the Internet at http://pubs.acs.org.
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Author Information
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Corresponding Author
*Email: rfernand@chem.iitb.ac.in
Notes
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The authors declare no competing financial interest.
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