Enantioselective dioxytosylation of styrenes using lactate-based chiral hypervalent iodine(III)

Article abstract of DOI:10.3762/bjoc.14.53

A series of optically active hypervalent iodine(III) reagents prepared from the corresponding (R)-2-(2-iodophenoxy)propanoate derivative was employed for the asymmetric dioxytosylation of styrene and its derivatives. The electrophilic addition of the hype

Full text of DOI:10.3762/bjoc.14.53

Enantioselective dioxytosylation of styrenes using lactate-
based chiral hypervalent iodine(III)
Morifumi Fujita*, Koki Miura and Takashi Sugimura
Letter
Open Access
Address:
Beilstein J. Org. Chem. 2018, 14, 659–663.
Graduate School of Material Science, University of Hyogo, Kohto,
Kamigori, Hyogo 678-1297, Japan
doi:10.3762/bjoc.14.53
Received: 25 December 2017
Accepted: 06 March 2018
Published: 20 March 2018
Email:
Morifumi Fujita* - fuji@sci.u-hyogo.ac.jp
*
Corresponding author
This article is part of the Thematic Series "Hypervalent iodine chemistry in
organic synthesis".
Keywords:
,2-difunctionalization of alkenes; enantioselective synthesis;
1
Guest Editor: T. Wirth
hypervalent iodine; oxidation
©
2018 Fujita et al.; licensee Beilstein-Institut.
License and terms: see end of document.
Abstract
A series of optically active hypervalent iodine(III) reagents prepared from the corresponding (R)-2-(2-iodophenoxy)propanoate de-
rivative was employed for the asymmetric dioxytosylation of styrene and its derivatives. The electrophilic addition of the hyperva-
lent iodine(III) compound toward styrene proceeded with high enantioface selectivity to give 1-aryl-1,2-di(tosyloxy)ethane with an
enantiomeric excess of 70–96% of the (S)-isomer.
Findings
Hypervalent aryl-λ3-iodanes have been widely used for metal- iodine compounds. As a seminal example in this field, Wirth et
free oxidation with high selectivity in organic synthesis [1-3]. al. [15-17] reported the dioxytosylation of styrene (1a,
The reactivity of an aryl-λ3-iodane is controlled by the elec- Scheme 1). Chiral hypervalent iodine reagents 2 bearing a
tronic and steric properties of the aryl group and the 1-methoxyethyl side chain were used for enantiocontrol of the
heteroatomic ligand coordinated to the iodine atom. Optically dioxytosylation, and the maximum enantiomeric excess (ee) of
active hypervalent iodine compounds contain chiral ligands or the product 3a reached 65%. Despite recent rapid progress in
chiral aryl groups. Several types of optically active hypervalent the field of asymmetric oxidation achieved by chiral hyperva-
iodine reagents and catalysts have been developed for highly lent iodine compounds, there has been no subsequent examina-
stereocontrolled oxidative transformations [4-14]. The enantio- tion of dioxytosylation, which can be used as a standard reac-
selective vicinal difunctionalization of alkenes constitutes one tion for comparing the enantiocontrolling ability of chiral
type of attractive transformation achieved by chiral hypervalent hypervalent iodine reagents.
659

Beilstein J. Org. Chem. 2018, 14, 659–663.
(
Table 1, entries 6–8). In the reactions of o-methylstyrene (1c),
the ee of the 1,2-dioxytosylated product 3c was slightly higher
than those of 3a and 3b, but the regioselectivity for 3c over 5c
was poor (Table 1, entries 9 and 10).
Scheme 2 illustrates possible reaction pathways that lead to 3
and the achiral byproduct 5. The treatment of
(
diacetoxyiodo)benzene with TsOH readily gives Koser’s
reagent [PhI(OH)OTs] [51], which has a higher electrophilicity
toward the carbon–carbon double bond in 1. The dioxytosyla-
tion of alkenes with Koser’s reagent was found to proceed via
an SN2 reaction of a cyclic intermediate such as I1, judging
Scheme 1: Enantioselective dioxytosylation of styrene as a seminal
example.
The design of chiral hypervalent iodine reagents using a lactate from the syn selectivity of the dioxytosylation [52,53]. The
motif has been employed for several types of oxidation reaction attack of the tosylate ion on I1 possibly takes place at the
since we first reported this procedure [18]. Enantioselective oxi- benzylic position or at the methylene carbon atom. The positive
dative transformations include the dearomatization of phenols charge of I1 may be stabilized by the aryl group and localized at
[
19-24], α-functionalization of carbonyl compounds [25-29], the benzylic position. This may allow the preferential forma-
and vicinal difunctionalization of alkenes [18,30-50]. Here, the tion of I3 from I1. If I2 was the major intermediate in the path-
efficiency of the lactate-based chiral hypervalent iodine way leading to 3, the stereochemical purity of 3 would have de-
reagents 4a–e (Figure 1) was assessed using the dioxytosyla- creased owing to the facile elimination of the iodonium group
tion of styrenes as a reference reaction.
[54] at the benzylic position of I2 (SN1). The high enantiomeric
ratio of 3 can be rationalized via a preference for the I1→I3→3
A series of lactate-derived aryl-λ3-iodanes 4a–e was used for pathway over the I1→I2→3 pathway. The product ratio of 3 to
the oxidation of styrenes 1 in the presence of p-toluenesulfonic 5 was affected by the ring substituent in styrenes 1: the elec-
acid (TsOH) in dichloromethane. The reaction proceeded at tron-withdrawing chloro substituent in 1b increased the amount
−
50 °C to give the 1,2-dioxytosylated product 3 and the rear- of 3, whereas the electron-donating methyl substituent in 1c de-
ranged product 5. The yields of 3 and 5 were determined by 1H creased the amount of 3. An electron-donating aryl group in-
NMR using an internal standard. The ee of 3 was determined by creases the rate of participation of the aryl group (I3→I4). In
chiral HPLC analysis. The results for the yields and ee are sum- other words, a reaction pathway that bifurcates from I3 to 3 and
marized in Table 1.
5 agrees well with the regioselectivity for 3 over 5 observed for
the substituted styrenes. The phenonium cation intermediate I4
The reaction of styrene (1a) with 4a gave the 1,2-dioxytosy- contains two reaction sites on the ethylene bridge. Electron
lated product 3a with 70% ee of the (S)-isomer (Table 1, entry donation due to the lone pair on the oxygen atom of the internal
1
). An ee of equal to or greater than 70% was also achieved in tosyloxy group may weaken the bond between the tosyloxy-
the reactions with the other lactate-based reagents 4b–e bonded carbon and the quaternary carbon in I4.
Table 1, entries 2–5). The reaction with the 2,6-bis(lactate)aryl
(
reagent 4e provided a high ee of 92%. The reactions of The reaction of styrene with 4a–e preferentially gave (S)-3,
p-chlorostyrene (1b) gave 3b with a similar ee, and the ratios of which forms via an electrophilic addition of the iodane toward
3
to 5 (3b to 5b) were higher than those in the reaction of 1a the Si face of styrene, followed by an SN2 reaction with the
Figure 1: Series of lactate-based hypervalent iodine reagents.
660

Beilstein J. Org. Chem. 2018, 14, 659–663.
Table 1: Enantioselective dioxytosylation of styrenes 1 using aryl-λ3-iodanes 4.a
Yield (%)b
Entry
Substrate
Reagent
4a
3
5
ee of 3 (%)c,d
70 (S)
80 (S)
78 (S)
70 (S)
92 (S)
70
1
2
3
4
5
6
7
8
9
1a (X = H)
53
49
41
41
80
63
46
79
7
15
16
14
22
20
6
1a (X = H)
4b
1a (X = H)
4c
1a (X = H)
4d
1a (X = H)
4e
1b (X = p-Cl)e
1b (X = p-Cl)e
1b (X = p-Cl)e
1c (X = o-Me)
1c (X = o-Me)
4a
4b
5
76
4e
5
90
4a
34
35
79
10
4e
10
96
aThe reaction was carried out at −50 °C in dichloromethane containing 4 (47 mM), TsOH (86 mM), and 1 (43 mM) for 4 h. bThe yield was determined
by 1H NMR using an internal standard. cThe ee was determined by chiral HPLC using a Daicel CHIRALPAK AD column (ø 4.6 mm × 250 mm).
dPreferential configuration of product 3. The absolute stereochemistry of 3b and 3c was not determined. eThe reaction was carried out for 20 h.
tosylate ion. If an SN1 mechanism were involved in the oxyto- preceding reactions [14], which include the diacetoxylation
sylation of I1, the enantiomeric ratio of 3 would decrease owing [38,39,50] and diamination [30,49] of styrene.
to the planar structure of the benzylic cation. Thus, the tosylate
ion may act as an effective nucleophile for the SN2 reaction of In summary, the reaction of styrenes with lactate-derived aryl-
I1. The stereoface-differentiation in the dioxytosylation reac- λ3-iodanes gave the dioxytosylated product with an ee of
tion using the lactate-derived aryl-λ3-iodanes is similar to that in 70–96%.
Scheme 2: Plausible pathways in dioxytosylation of styrenes.
661

Beilstein J. Org. Chem. 2018, 14, 659–663.
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Supporting Information File 1
2
Experimental procedures, characterization data, and copies
of 1H and 13C NMR spectra are available.
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