Geminal difunctionalization of vinylarenes: Concise synthesis of 1,3-dioxolan-4-ones

Article abstract of DOI:10.1055/s-0039-1690250

We report a straightforward method for the synthesis of five-membered 1,3-dioxolan-4-ones by an unprecedented oxidative alkene geminal difunctionalization strategy using α-hydroxy carboxylic acids. Under the geminal oxidative addition conditions, various substituted α-hydroxy carboxylic acids and styrenes containing a variety of substituents, including β-substituted styrenes, were effectively coupled regioselectively (anti-Markovnikov) with an isobutyl-substituted chiral α-hydroxy carboxylic acid, providing an annulation with excellent dia?-?-stereoselectivity. An aryl migration in the semipinacol rearrangement leading to geminal oxidative addition of the α-hydroxy carboxylic acids was confirmed by deuterium-labelling and control studies.

Full text of DOI:10.1055/s-0039-1690250

SYNLETT
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© Georg Thieme Verlag Stuttgart · New York
2019, 30, 2263–2267
letter
2263
en
P. V. Balaji, S. Chandrasekaran
Letter
Synlett
Geminal Difunctionalization of Vinylarenes: Concise Synthesis of
1,3-Dioxolan-4-ones
Pandur Venkatesan Balaji
R1
R1
OH
NBS, AgOTf
CH2Cl2, rt
O
Srinivasan Chandrasekaran*
0
0
0
0-0
0
0
1-6
4
8
7-
5
3
5
7
+
Ar
Ar
O
O
OH
O
Department of Organic Chemistry, Indian Institute of Science,
Bangalore-560012, Karnataka, India
scn@iisc.ac.in
18 examples
up to 90% yield
1,3-Dioxolan-4-ones from olefins
Aryl migration
Regioselective anti-Markovnikov
geminal addition
Deuterium-labelling studies
Received: 08.08.2019
Accepted after revision: 22.10.2019
Published online: 06.11.2019
have been used as powerful tools in syntheses of complex
natural products and in stereocontrolled polymerizations.8,9
Moreover the 1,3-dioxolan-4-one moiety is also found as a
key structural motif in many bioactive natural products.10
Five-membered 1,3-dioxolan-4-ones are conventionally
synthesized by Lewis or Brønsted acid mediated condensa-
tion of -hydroxy carboxylic acids with aldehydes.1c,2 Ow-
ing to the importance of 1,3-dioxolan-4-ones as useful syn-
thons, various methods have been developed for their syn-
thesis by using such Lewis or Brønsted acids as Bi(NO3)2,
BF3·OEt2, I2, TsOH, TfOH, or MsOH, or dehydrating agents,
such as P2O5, under microwave conditions (Scheme 1A).11
Yamamoto and co-workers have developed a highly effi-
cient and diastereoselective Sc(OTf)3/Sc(NTf)3-catalyzed
condensation of chiral -hydroxy carboxylic acids with al-
dehydes or ketones.12 Senanayake and co-workers investi-
gated in detail the factors that control the diastereoselectiv-
ity of the condensation, and they developed a multikilo-
gram protocol for the synthesis of (S)-cyclohexyl-
DOI: 10.1055/s-0039-1690250; Art ID: st-2019-l0417-l
Abstract We report a straightforward method for the synthesis of
five-membered 1,3-dioxolan-4-ones by an unprecedented oxidative
alkene geminal difunctionalization strategy using -hydroxy carboxylic
acids. Under the geminal oxidative addition conditions, various substi-
tuted -hydroxy carboxylic acids and styrenes containing a variety of
substituents, including -substituted styrenes, were effectively coupled
regioselectively (anti-Markovnikov) with an isobutyl-substituted chiral
-hydroxy carboxylic acid, providing an annulation with excellent dia-
stereoselectivity. An aryl migration in the semipinacol rearrangement
leading to geminal oxidative addition of the -hydroxy carboxylic acids
was confirmed by deuterium-labelling and control studies.
Key words dioxolanones, geminal difunctionalization, regioselectivi-
ty, rearrangement, aryl migration
Installation of new chiral centers or stereoselective
transformation using a chiral auxiliary (the chiral pool ap-
proach) remains an attractive and powerful strategy in or-
ganic synthesis. Because of its effectiveness in stereocontrol
and its broad applicability, the chiral pool approach has
been routinely employed in stereoselective syntheses of en-
antiopure compounds, despite the emergence of efficient
catalytic asymmetric synthetic methods. The five-mem-
bered chiral 1,3-dioxolan-4-one unit is among the most
highly privileged and most widely used chiral scaffolds in
asymmetric synthesis.1 The remarkable work of Seebach
and co-workers, illustrating the power of self-regeneration
of stereoisomers has popularized the use of dioxolanones as
chiral auxiliaries in asymmetric synthesis.2,3 Due to their ef-
fectiveness in generating new stereogenic centers, chiral
1,3-dioxolan-4-ones are widely used in syntheses of a vari-
ety of chiral building blocks, especially through -function-
alizations of carbonyl groups,2a,b,4 the Petasis–Ferrier rear-
rangement,5 cycloadditions,6 and radical reactions.7 These
A. Conventional method: condensation with aldehydes
R1
R1
OH
OH
Lewis/
Brønsted Acid
O
O
+
R2
H
O
R2
O
O
B. Intramolecular tethered lactonization
Ph
Ph
O
O
Lewis/
Brønsted Acid
O
O
R2
OH
O
C. This work: geminal difunctionalization of vinylarenes
(anti-Markovnikov addition)
R1
R1
O
OH
OH
[Br]+
O
+
Ar
Ar
O
O
Scheme 1 Approaches to the synthesis of 1,3-dioxolan-4-ones
© 2019. Thieme. All rights reserved. Synlett 2019, 30, 2263–2267
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

2264
P. V. Balaji, S. Chandrasekaran
Letter
Synlett
(phenyl)glycolic acid.13 Although variety of efficient meth-
ods has been reported for the synthesis of 1,3-dioxolan-4-
ones, most of them rely on a dehydrative acetal-type con-
densation between an aldehyde and an -hydroxy carbox-
ylic acid mediated either by activation of the carbonyl
group or by dehydration.
acids 1b–e, containing various substituents at the -posi-
tion, reacted smoothly with styrene (2a) (NBS, AgOTf,
CH2Cl2, 1 h, rt) to give good yields of the corresponding 1,3-
dioxolan-4-ones 3b–e. Interestingly, the chiral -hydroxy
carboxylic acid 1f containing a 2-butyl group derived from
L-isoleucine, on reaction with styrene, afforded a single di-
astereomer of the 1,3-dioxolan-4-one 3f exclusively and in
a good yield. The disubstituted and unsubstituted -hy-
droxy carboxylic acids 1g and 1h, respectively, also under-
went efficient geminal addition reactions with styrene to
furnish the corresponding 1,3-dioxolan-4-ones 3g and 3h
as sole products with good regioselectivity.
Intriguingly, however, only a few methods are available
based on other approaches. 1,3-Dioxolan-4-ones have also
been obtained by protic-acid-mediated or Cu(OTf)2- or
Al(OTf)2-catalyzed intramolecular lactonization through ad-
dition of a tethered carboxylic acid to an alkene, and also by
aldol-type addition of a carbonyl group to an akene through
tethered lactonization of a carboxylic acid (Scheme 1B).14
Dixneuf and co-workers reported an elegant and highly di-
astereoselective Ru(II)-catalyzed addition of -hydroxy car-
boxylic acids to terminal alkynes for the synthesis of 1,3-di-
oxolan-4-ones.15 Despite the high utility of 1,3-dioxolan-4-
ones in organic synthesis, there are few alternative meth-
ods to the condensation reaction for the synthesis. In this
context, we report a concise method for the synthesis of
1,3-dioxolan-4-ones through oxidative difunctionalization
of olefins, mediated by bromonium ion, in a highly regiose-
lective manner (Scheme 1C).
We recently reported that vinylarenes can be oxidative-
ly difunctionalized in a stereoselective manner by haloni-
um-mediated methods, providing straightforward access to
nitrogen- or oxygen-containing heterocycles.16 With our
continued interest in oxidative geminal difunctionalization
of alkenes, and with the scarcity of available methods for
the synthesis of 1,3-dioxolan-4-ones, we surmised that suc-
cessful geminal addition of -hydroxy carboxylic acids to
alkenes might provide a concise access to 1,3-dioxolan-4-
ones directly from alkenes. Accordingly, when we treated
(R)-(–)-mandelic acid (1a), an -hydroxy carboxylic acid,
with styrene (2a) under our prototype bromonium ion me-
diated conditions (NBS, AgOTf, CH2Cl2, 1 h, rt),16a we were
pleased to observe that the 1,3-dioxolan-4-one product 3a
was obtained in a good yield through geminal addition, al-
beit as a mixture of diastereomers (Scheme 2)
Table 1 Geminal Addition of Substituted -Hydroxy Carboxylic Acids
to Styrene (2a)
R
R
O
OH
OH
NBS, AgOTf
O
*
+
H
CH2Cl2
rt, 1 h
O
Ph
2a
Ph
O
1b–h
3b–h
CH3
O
H3C
H3C
H3C
O
H3C
O
*
O
*
H
H
H
*
O
O
Ph
Ph
Ph
O
O
O
3b
63%, dr 66:37
CH3
3c
3d
72%, dr 55:45
61%, dr 62:38
H3C
CH3
Ph
H3C
O
*
O
*
O
O
H
H
H
O
H
O
O
O
Ph
Ph
Ph
Ph
O
O
O
O
3f
58%, dr >95:5
3e
54%, dr 58:42
3g, 65%
3h, 48%
Reaction conditions: 1 equiv (0.50 mmol) of corresponding α-hydroxy acid 1a–h,
1.5 equiv of 2a, 1.2 equiv of NBS, 1.4 equiv of AgOTf, 5 mL of CH2Cl2. Isolated yields
We then examined the effects of substituents on the
styrene on the geminal oxidative addition reaction (Table
2). Styrenes 2i–l containing alkyl substituents at the ortho-,
meta- or para-positions, on reaction with the -hydroxy
carboxylic acid 1g, afforded good yields of the correspond-
ing 1,3-dioxolan-4-ones 3i–l through geminal addition (Ta-
ble 2, entries 1–4). Interestingly, styrenes 2m and 2n, con-
taining electron-withdrawing substituents, also reacted ef-
fectively with the -hydroxy carboxylic acid 1g to furnish
the 1,3-dioxolan-4-ones 3m and 3n, respectively, under the
same oxidative conditions (NBS, AgOTf, CH2Cl2, rt, 1 h) (en-
tries 5 and 6). The -substituted styrenes, cis- and trans-
stilbenes 2o and 2p, respectively, on reaction with -hy-
droxy carboxylic acid 1g both gave the 1,3-dioxolan-4-one
3o as the sole product (entries 7 and 8). Similarly, the cis-
and trans- -methyl styrenes 2q and 2r, on reaction with -
hydroxy carboxylic acid 1g, also both gave the single 1,3-di-
oxolan-4-one 3q as the sole product (entries 9 and 10).
Ph
Ph
O
OH
OH
NBS, AgOTf
O
*
+
CH2Cl2, rt, 1 h
76%, dr 50:50
H
Ph
O
Ph
O
1a
2a
3a
Scheme 2 Synthesis of a 1,3-dioxolan-4-one through a geminal addi-
tion to styrene (2a)
Encouraged by these results, which demonstrated the
feasibility of a straightforward synthesis of 1,3-dioxolan-4-
ones from styrene through geminal addition, we decided to
study the scope of the reaction further. First, we studied the
effects on the geminal addition of substituents on the -hy-
droxy carboxylic acid (Table 1). The -hydroxy carboxylic
© 2019. Thieme. All rights reserved. Synlett 2019, 30, 2263–2267

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P. V. Balaji, S. Chandrasekaran
Letter
Synlett
Table 2 Geminal Addition of -Hydroxy Carboxylic Acid 1g to Substi-
tuted Styrenes
styrene (2a) (NBS, AgOTf, CH2Cl2, rt, 1 h), formed only the
vicinal addition products 5 and 7, respectively (Scheme 3, A
and B), and did not give geminal addition products, where-
as alcohol 8, under the same reaction conditions, formed
the geminal addition product 9 exclusively (Scheme 3C),
showing that the regioselectivity is dependent on the na-
ture of the nucleophile being added.
CH3
H3C
H3C
NBS, AgOTf
OH
OH
H3C
O
O
R
+
CH2Cl2
rt, 1 h
H
R
O
O
1g
2i–r
3i–r
Yield (%)b
Entry
1
Styrene
Product
CH3
Standard Conditions
Ph
Ph
O
OH
OH
NBS, AgOTf
H3C
O
O
*
+
H
H
CH2Cl2, rt, 1 h
76%, dr 50:50
Ph
58
O
O
2i
Ph
O
O
H3C
3i
1a
2a
3a
H3C
CH3
Control Experiments
H3C
O
O
H
2
3
[A] Nu: Ar-COOH, Vicinal Addition
61
57
O
2j
3j
CH3
COOH
O
O
CH3
NBS, AgOTf
CH3
O
Ph
O
+
H3C
O
Ph
Ph
O
CH2Cl2, rt
1 h, 68%
Ph
2a
H
H
H
CH3
CH3
2k
2l
O
4
5
3k
[B] Nu: Ar-CH2-COOH, Vicinal Addition
CH3
H3C
O
CH3
CH3
CH3
O
CH3
CH3
O
O
4
5
67
COOH
NBS, AgOTf
O
O
O
CH2Cl2, rt
1 h, 54%
+
CH3
p-Tol
3l
Ph
2a
Ph
p-Tol
CH3
6
7
H3C
O
O
62
Br
F
CH3
Br
F
O
2m
[C] Nu: R-CH2-OH, Geminal Addition
3m
Ph
3
CH3
NBS, AgOTf
O
O
H3C
O
O
+
6
7
60
65
CH2Cl2, rt
1 h, 52%
Ph
OH
H
H
Ph
2a
Ph
3
2n
O
3n
Ph
8
9
CH3
H3C
O
O
Scheme 3 Control experiments
Ph
Ph
Ph
O
2o
3o
Ph
The reaction of ,-dideuterostyrene (2s) with -hy-
droxy carboxylic acid 1g provided the dideuterobenzyl-
substituted 1,3-dioxolan-4-one 3s as the sole product in
good yield (Scheme 4).
CH3
H3C
O
Ph
8
9
86
72
90
H
H
2p
Ph
O
Ph
Ph
O
3o
Ph
CH3
CH3
H3C
H3C
β
H3C
O
D
H
D
O
OH
OH
H3C
O
O
NBS, AgOTf
H3C
2q
+
α
H
Ph
CH2Cl2, rt
1 h, 63%
O
Ph
α
O
Ph
O
β
3q
H3C
D
3s
1g
2s
D
CH3
H3C
O
Scheme 4 Deuterium-labelling studies
O
Ph
H
10
CH3
Ph
O
2r
3q
A plausible mechanism for the geminal oxidative addi-
tion reaction, based on the control studies and the deuteri-
um-labelling study, is presented in Scheme 5. Activation of
alkene 2s by formation of bromonium ion, followed by the
regioselective ring-opening addition of the hydroxy group
of 1g provides the -bromo benzylic ether I-1. The forma-
tion of the dideuterobenzyl-substituted 1,3-dioxolan-4-one
3s (see Scheme 4) as the only product in the addition reac-
tion of ,-dideuterostyrene (2s) clearly demonstrates that
H3C
a Reaction conditions: same as Table 1. b Isolated yields.
To gain some mechanistic insights into the geminal oxi-
dative addition of -hydroxy carboxylic acids to vinyl-
arenes, we conducted control experiments using carboxylic
acids and an alcohol as mononucleophiles (Scheme 3). The
alkyl and the aryl carboxylic acids 4 and 6, on reaction with
© 2019. Thieme. All rights reserved. Synlett 2019, 30, 2263–2267

2266
P. V. Balaji, S. Chandrasekaran
Letter
Synlett
phenonium ion
H
O
Ag
D
β
D
O
OH
OH
β
D
β
OH
D
H
D
O
NBS
D
Br
H
O
+
+
α
H3C
H3C
1g
H3C
H3C
AgOTf
α
α
O
H3C
Ph
O
Ph
H
CH3
2s
anchimeric
assistance
I–2
I–1
phenyl migration
O
H
O
D
D
O α
D
O
H3C
H3C
H3C
H3C
H
β Ph
β
Ph
O
α
I–3
O
H
D
3s
Scheme 5 Plausible pathway for the geminal addition of -hydroxy carboxylic acids to a vinylarene
the reaction follows a single pathway involving the forma-
tion of phenonium ion I-2 and subsequent migration of the
phenyl group from the benzylic (-position) to the methy-
lene (-position) driven by the formation of the oxonium
ion intermediate I-3 (Scheme 5). Furthermore, this is in ac-
cordance with the observed dependence of the regioselec-
tivity on the nature of the nucleophile being added (cf.
Scheme 3, B and C). This indicates the essential role of the
functional group in the formation of a favorable carboca-
tion through neighboring-group participation, thereby con-
trolling the regioselectivity of the addition process. Eventu-
ally, the tethered carboxylic acid adds to the oxonium ion I-
3 to form the 1,3-dioxolan-4-one 3s in an overall geminal
addition process.
In summary, a, bromonium-ion-mediated, straightfor-
ward synthesis of 1,3-dioxolan-4-ones has been developed
through highly regioselective (anti-Markovnikov) geminal
addition of -hydroxy carboxylic acids to vinylarenes.17 In
this unprecedented approach, the reaction proceeds
through geminal oxidative dioxygenation of a hydrocarbon
(olefin) facilitated by NBS and AgOTf, in which two new C–
O bonds are formed. This geminal addition works efficient-
ly with various substituted -hydroxy carboxylic acids to
provide 1,3-dioxolan-4-ones in good yields. Moreover, a
chiral -hydroxy carboxylic acid derived from isoleucine,
which contained a 2-butyl substituent at the -position,
formed the corresponding annulation product with excel-
lent diastereoselectivity. The -hydroxy carboxylic acids
added effectively to variety of substituted styrenes with
complete regioselectivity. Control studies using carboxylic
acids and alcohols as nucleophiles exclusively gave vicinal
and geminal addition products, respectively. This supports
the essential role of neighboring-group-participation-facili-
tated formation of an oxonium ion in achieving selective
geminal addition in a highly regioselective manner. The in-
volvement of aryl-group migration leading to geminal oxi-
dative addition was confirmed by deuterium-labelling
studies.
Acknowledgment
P.V.B. thanks IISc, Bangalore, CSIR-New Delhi, and JNCASR, Jakkur, for
research fellowships. S.C.N. thanks the Indian National Science Acade-
my, New Delhi, for the award of an INSA Distinguished Professorship.
Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0039-1690250.
S
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D.; Liermann, J. C.; Sandjo, L. P.; Berkelmann-Löhnertz, B.;
Opatz, T.; Thines, E. Phytochemistry 2013, 89, 96.
(11) For representative recent synthesis of 1,3-dioxolan-4-ones
using condensation methods, see: (a) Pearson, W. H.; Cheng, M.
C. J. Org. Chem. 1987, 52, 1353. (b) Orthland, J.-Y.; Vicart, N.;
Greiner, A. J. Org. Chem. 1995, 60, 1880. (c) Grover, P. T.;
Bhongle, N. N.; Wald, S. A.; Senanayake, C. H. J. Org. Chem. 2000,
65, 6283. (d) Srivastava, N.; Dasgupta, S. K.; Banik, B. K. Tetrahe-
dron Lett. 2003, 44, 1191. (e) Ferrett, R. R.; Hyde, M. J. Lahti K. A.;
Friebe, T. L. Tetrahedron Lett. 2003, 44, 2573. (f) Banik, B. K.;
Chapa, M.; Marquez, J.; Cardona, M. Tetrahedron Lett. 2005, 46,
2341. (g) Misaki, T.; Ureshino, S.; Nagase, R.; Oguni, Y.; Tanabe,
Y. Org. Process Res. Dev. 2006, 10, 500. (h) Nagase, R.; Oguni, Y.;
Misaki, T.; Tanabe, Y. Synthesis 2006, 3915. (i) Boyko, V. I.; Rodik,
R. V.; Severenchuk, I. N.; Voitenko, Z. V.; Kalchenkoa, V. I. Syn-
thesis 2007, 2095. (j) Chehidi, I.; Amanetoullah, A. O.;
Chaabouni, M. M.; Baklouti, A. J. Fluorine Chem. 2010, 131, 66.
(k) Küçük, H. B. Tetrahedron Lett. 2015, 56, 5583.
(18) 1,3-Dioxolan-4-ones 3a–s; General Procedure
NBS (0.60 mmol) and AgOTf (0.70 mmol) were added to a well-
stirred colorless solution of the appropriate -hydroxy carbox-
ylic acid 1 (0.50 mmol) and the appropriate styrene 2 (0.75
mmol) in CH2Cl2 (5 mL) at rt (25 °C) under argon in a dry
Schlenk flask. The mixture initially changed from colorless to
cloudy white, then to colorless with a pale-yellow suspension,
and finally to colorless with a pale-gray precipitate after 1 h.
The progress of the reaction was monitored by TLC. The mixture
was stirred for 1 h at rt, then H2O (3 mL), sat. aq NaHCO3 (4 mL),
and sat. aq Na2S2O3 (4 mL) were added successively. The mixture
was extracted with CH2Cl2 (3 × 5 mL), and the combined organic
layers were dried (Na2SO4), filtered, and concentrated in vacuo.
The crude product was purified by flash chromatography [silica
gel, pentane–Et2O (25:1)].
(5R)-2-Benzyl-5-phenyl-1,3-dioxolan-4-one (3a)
Yield: 97 mg (76%).
Diastereomer A: white solid; mp 82–84 °C; []D –89.7 (c 1.0,
CHCl3). IR (thin film): 3032, 2924, 1796, 1496, 1454, 1401, 1274,
1214 cm–1. 1H NMR (400 MHz, CDCl3):  = 7.36–7.21 (m, 10 H),
5.86 (t, J = 4.5 Hz, 1 H), 5.19 (s, 1 H), 3.30–3.20 (m, 2 H). 13C NMR
(100 MHz, CDCl3):  = 171.3, 133.5, 133.0, 130.2, 129.2, 128.6,
128.5, 127.3, 127.0, 103.9, 76.8, 40.5. HRMS (ESI-QTOF): m/z [M
+ Na]+ calcd for C16H14NaO3: 277.0841; found: 277.0843.
24
24
Diastereomer B: white solid; mp 53–54 °C; []D –38.2 (c 1.0,
(12) Ishihara, K.; Karumi, Y.; Kubota, M.; Yamamoto, H. Synlett 1996,
839.
CHCl3). IR (thin film): 3031, 2924, 1797, 1495, 1454, 1215, 1177,
1109, 992, 934 cm–1 1H NMR (400 MHz, CDCl3):  = 7.38–7.25
.
(13) Su, X.; Bhongle, N. N.; Pflum, D.; Butler, H.; Wald, S. A.; Bakale,
R. P.; Senanayake, C. H. Tetrahedron: Asymmetry 2003, 14, 3593.
(14) For selected examples, see: (a) Eberle, M. K.; Kahle, G. G. J. Am.
Chem. Soc. 1977, 99, 6038. (b) Faunce, J. A.; Friebe, T. L.; Grisso,
B. A.; Losey, E. N.; Sabat, M.; Mackenzie, P. B. J. Am. Chem. Soc.
1989, 111, 4508. (c) Faunce, J. A.; Crisso, B. A.; Mackenzie, P. B.
J. Am. Chem. Soc. 1991, 113, 3418. (d) Chaminade, X.; Coulombel,
L.; Olivero, S.; Dunach, E. Eur. J. Org. Chem. 2006, 3554.
(e) Burghart-Stoll, H.; Brückner, R. Eur. J. Org. Chem. 2012, 3978.
(15) Nexeux, M.; Seiller, B.; Hagedorn, F.; Bruneau, C.; Dimeuf, P. H.
J. Organomet. Chem. 1993, 451, 133.
(m, 10 H), 6.02 (t, J = 3.9 Hz, 1 H), 5.11 (s, 1 H), 3.21 (d, J = 4.2 Hz,
2 H). 13C NMR (100 MHz, CDCl3):  = 164.1, 126.6, 126.0, 123.2,
122.0, 121.9, 121.6, 120.4, 118.9, 97.9, 68.3, 34.3. HRMS (ESI-
QTOF): m/z [M + Na]+ calcd for C16H14NaO3: 277.0841; found:
277.0850.
2-Benzyl-5,5-dimethyl-1,3-dioxolan-4-one-d2 (3s)
Colorless oil; yield: 66 mg (63%). IR (thin film): 2984, 2926,
1798, 1387, 1281, 1183, 1008, 986 cm–1 1H NMR (400 MHz,
.
CDCl3):  = 7.34–7.25 (m, 5 H), 5.72 (s, 1 H, HCCD2Ph), 1.38 (s, 3
H), 1.34 (s, 3 H). 13C NMR (100 MHz, CDCl3):  = 175.4, 133.3,
3
130.1, 128.4, 127.2, 101.9, 77.2, 40.4 (quint, JC–D = 19.6 Hz),
24.4, 21.8. HRMS (ESI-QTOF): m/z [M
12H12D2NaO3: 231.0966; found: 231.0969.
+
Na]+ calcd for
C
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