Enantio- and diastereoselective cyclopropanation with tert-butyl α-diazopropionate catalyzed by dirhodium(II) tetrakis[N- tetrabromophthaloyl-(S)-tert-leucinate]

Article abstract of DOI:10.1016/j.tetlet.2011.06.008

The first successful example of a catalytic asymmetric cyclopropanation with α-diazopropionates is described. The cyclopropanation reaction of 1-aryl-substituted and related conjugated alkenes with tert-butyl α-diazopropionate has been achieved by catalysis with dirhodium(II) tetrakis[N-tetrabromophthaloyl-(S)-tert-leucinate], Rh₂(S-TBPTTL) ₄, providing the corresponding cyclopropane products containing a quarternary stereogenic center in good to high yields and with high diastereo- and enantioselectivities (trans:cis = 90:10 to >99:1, 81-93% ee).

Full text of DOI:10.1016/j.tetlet.2011.06.008

Tetrahedron Letters 52 (2011) 4200–4203
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Tetrahedron Letters
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Enantio- and diastereoselective cyclopropanation
with tert-butyl
a-diazopropionate catalyzed by dirhodium(II)
tetrakis[N-tetrabromophthaloyl-(S)-tert-leucinate]
Takayuki Goto a,b, Koji Takeda a, Masahiro Anada a, Kaori Ando c, Shunichi Hashimoto a,
⇑
a Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo 060 0812, Japan
b Development Research Laboratories, Kyorin Pharmaceutical Co., Ltd, 1848, Nogi, Nogi-machi, Shimotsuga-gun, Tochigi 329 0114, Japan
c Department of Chemistry, Faculty of Engineering, Gifu University, Yanagido 1-1, Gifu 501 1193, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
The first successful example of a catalytic asymmetric cyclopropanation with
described. The cyclopropanation reaction of 1-aryl-substituted and related conjugated alkenes with tert-
butyl -diazopropionate has been achieved by catalysis with dirhodium(II) tetrakis[N-tetrabromophtha-
loyl-(S)-tert-leucinate], Rh2(S-TBPTTL)4, providing the corresponding cyclopropane products containing a
quarternary stereogenic center in good to high yields and with high diastereo- and enantioselectivities
(trans:cis = 90:10 to >99:1, 81–93% ee).
a-diazopropionates is
Received 16 May 2011
Revised 1 June 2011
Accepted 3 June 2011
Available online 12 June 2011
a
Keywords:
Ó 2011 Elsevier Ltd. All rights reserved.
Asymmetric catalysis
Cyclopropanation
Dirhodium(II) complex
a-Alkyl-
a-diazoester
Carbene
Substituted cyclopropanes are commonly encountered struc-
tural subunits in a wide variety of biologically important natural
products and medicinal agents.1 Since the pioneering work of
Nozaki and Noyori in 1966,2 the transition metal-catalyzed asym-
metric cyclopropanation of alkenes with diazo compounds has
emerged as one of the most direct and efficient routes to optically ac-
tive cyclopropane building blocks.3 Over the past two decades, a
number of powerful catalytic systems based on Cu(I),4 Co(II),5
Rh(II),6 Ru(II),7 and Ir(III)8 complexes of well-designed chiral ligands
have been developed to achieve high enantio- and diastereoselectiv-
ity for cyclopropanation reactions with various types of diazo
compounds.9–20 While the majority of successful asymmetric cyclo-
propanations reported involved the use of acceptor-substituted dia-
zo compounds,4–8,10 most commonly diazoacetates,4–8 substantial
progress in this field has recently been achieved by expanding the
reaction scope to include donor/acceptor-substituted diazo com-
pounds11–14 such as vinyldiazoacetates11 and aryldiazoacetates,12
as well as acceptor/acceptor-substituted carbene precursors15–22
such as nitrodiazoacetates,15 nitrodiazoketones,16 amidodiazoace-
tates,17 cyanodiazoacetamides,18 diazomalonates19,20 and related
phenyliodinium ylide variants.21 However, asymmetric cyclopropa-
shift26 in metal-carbene intermediates until a recent breakthrough
by Fox et al.27 Fox et al. developed highly enantio-, diastereo-, and
chemoselective cyclopropanations of terminal aromatic alkenes
and benzofuran with a-alkyl-a-diazoesters using dirhodium(II) tet-
rakis[N-phthaloyl-(S)-tert-leucinate], Rh2(S-PTTL)4 (3a),28 as a chiral
catalyst in hexanes at ꢀ78 °C. While this work was a notable land-
mark, the enantioselectivity was highly sensitive to the structure
of the diazoester. Exceptionally high levels of enantioselectivity
Rh2(S-PTTL)4 (3a)
R
CO2Et
(0.5 mol %)
R
CO2Et
Ph
+
hexanes, –78 °C
N2
5 (3 equiv)
5a R = Me
5b R = Et
5c R = nPr
Ph
4a
6
5d R = nBu
5e R = CH2CH2CHMe2
Me CO2Et
Et CO2Et nPr CO2Et nBu CO2Et
CO2Et
Ph
Ph
Ph Ph
Ph
6a
6b
6c
6d
6e
95% (68%)
91:9 dr
95% (76%) 100% (85%) 96% (84%)
92% (89%)
>95:5 dr
99% ee
92:8 dr
79% ee
>95:5 dr
94% ee
>95:5 dr
96% ee
nation with a-alkyl-a
-diazoesters23–25 has remained elusive due to
3% ee
the propensity to form
a,b-unsaturated esters via a 1,2-hydride
Scheme 1. Catalytic asymmetric cyclopropanation of styrene with
a-alkyl-a-
diazoesters catalyzed by Rh2(S-PTTL)4 reported by Fox.27 The isolated yields in
parentheses were obtained when 1.1 equiv of styrene and 1.0 equiv of diazoesters
were used.
⇑
Corresponding author. Tel.: +81 11 706 3236; fax: +81 11 706 4981.
E-mail address: hsmt@pharm.hokudai.ac.jp (S. Hashimoto).
0040-4039/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2011.06.008

T. Goto et al. / Tetrahedron Letters 52 (2011) 4200–4203
4201
Me
(up to 99% ee) in cyclopropanations of styrene were achieved with
diazoesters bearing larger -alkyl groups than the -ethyl substitu-
ent as the reaction with ethyl -diazopropionate (5a) and ethyl
Me CO2R
Ph
OH
LiAlH4
R
a
a
THF, 0 °C
98%
S
Ph
a
a-
8
6f R = CHiPr2
diazobutanoate (5b) gave the corresponding cyclopropane products
in 3% and 79% ee, respectively (Scheme 1).27 Very recently, we re-
ported the first example of catalytic asymmetric cyclopropenation
6g R = tBu
Scheme 2. Determination of the absolute stereochemistry of 6f and 6g.
of 1-alkynes with
a-alkyl-a
-diazoesters.29 In this process, Rh2(S-
TBPTTL)4 (3d), a brominated analog of Rh2(S-PTTL)4 (3a), emerged
as the catalyst of choice for achieving exceptionally high levels of
asymmetric induction (up to 99% ee) as well as good to high selectiv-
ities over alkene formation via a 1,2-hydride shift. As part of our
interest in further extension of the scope and utility of 3d, we now
Daicel Chiralpak IC column. The preferred absolute stereochemis-
try of 6f [½a 2D1
ꢀ104.2 (c 1.01, CHCl3) for 84% ee] was established
ꢁ
as 1R,2S by its transformation [LiAlH4, THF, 0 °C, 3 h] to the known
trans-1-phenyl-2-methylcyclopropane-1-methanol [½a D22
ꢀ15.4 (c
ꢁ
0.64, CHCl3); lit.,29
½
a 2D1
ꢁ
ꢀ17.2 (c 0.17, CHCl3) for 95% ee of
address the issue of enantiocontrol in cyclopropanations with a-dia-
zopropionates,25 a virtually unmet challenge in Fox’s cyclopropana-
tion methodology.27
(1R,2S)-enantiomer] (Scheme 2). We next evaluated the perfor-
mance of other dirhodium(II) carboxylates, Rh2(S-PTTL)4 (3a),28
Rh2(S-TFPTTL)4 (3b)30 and Rh2(S-TCPTTL)4 (3c).31,32 While all of
these catalysts provided the trans-cyclopropane 6f in high yields
and with the same sense of asymmetric induction and similar high
diastereoselectivity as those observed with Rh2(S-TBPTTL)4 (3d),
the highest level of enantioselectivity was only 69% ee, which
was obtained using Rh2(S-TCPTTL)4 (3c) (entries 1 vs 2–4). Clearly,
3d proved to be by far the best choice for this transformation as
well as for the asymmetric cyclopropenation reaction. An examina-
tion of the temperature profile demonstrated that lowering the
reaction temperature from ꢀ60 to ꢀ78 °C resulted in perfect
trans-diastereoselectivity, though catalysis at ꢀ78 °C required a
significantly longer reaction time to reach completion and resulted
in 86% ee (entry 5). Not unexpectedly, increasing the reaction tem-
perature to ꢀ40 or ꢀ20 °C was accompanied by a significant
decrease in enantioselectivity while maintaining high diastereose-
lectivity (75% and 66% ee, entries 6 and 7). Using Rh2(S-TBPTTL)4 as
a catalyst, the effect of the ester moiety was also evaluated at
ꢀ60 °C. While the use of ethyl ester 5a resulted in lower enantiose-
lectivity (35% ee, entry 8), the reaction with tert-butyl ester 5g
afforded the trans-cyclopropane product 6g as a single diastereo-
mer in high yield and with somewhat higher enantioselectivity
O
S
O
X
O
N
X
X
N
C12H25
O
H
X
H
O
H
O
O
O
O
N
CO2Me
O
Rh Rh
Rh Rh
Rh Rh
Rh2(4S-MEOX)4 (1)
Rh2(S-DOSP)4 (2)
X = H: Rh2(S-PTTL)4 (3a)
X = F: Rh2(S-TFPTTL)4 (3b)
X = Cl: Rh2(S-TCPTTL)4 (3c)
X = Br: Rh2(S-TBPTTL)4 (3d)
Based on our previous work,29 we initially explored the cyclo-
propanation of styrene (4a) (4 equiv) with 2,4-dimethyl-3-pentyl
a-diazopropionate (5f) using 1 mol % of Rh2(S-TBPTTL)4 (3d) in
dichloromethane at ꢀ60 °C. The reaction proceeded to completion
within 7 h, giving the trans-cyclopropane product 6f in 92% yield
and 97:3 dr with no signs of the formation of alkene 7f (Table 1,
entry 1). As with the Rh2(S-TBPTTL)4-catalyzed cyclopropenation
system,29 no slow addition of 5f was required. The trans-stereo-
chemistry of 6f was established by 1H NOE between the C1 methyl
group and ortho protons on the benzene ring. The enantioselectiv-
ity of this reaction was determined to be 84% ee by HPLC using a
Table 1
Enantio- and diastereoselective cyclopropanation of styrene with
a
-diazopropionates catalyzed by dirhodium(II) carboxylatesa
2.5% NOE
Me CO2CHiPr2
Rh(II) complex
CO2R (1 mol %)
Me CO2R
Ph
H
Me
Ph
+
N2
5
CH2Cl2
4a (4 equiv)
6
6f
i
CO2R
7f
R = CH Pr2
t
7g
R = Bu
not detected
7a R = Et
Entry
a-Diazoesters
Rh(II) catalyst
Temp (°C)
Time (h)
Cyclopropanes
R
Yieldb (%)
trans:cisc
Eed (%)
1
2
3
4
5
6
7
8
5f
5f
5f
5f
5f
5f
5f
5a
5g
5g
5g
CHiPr2
Rh2(S-TBPTTL)4 (3d)
Rh2(S-PTTL)4 (3a)
ꢀ60
ꢀ60
ꢀ60
ꢀ60
ꢀ78
ꢀ40
ꢀ20
ꢀ60
ꢀ60
ꢀ78
ꢀ78
7
4
3
3
48
2
0.5
2
2
6
8
6f
6f
6f
6f
6f
6f
6f
6a
6g
6g
6g
92
89
86
89
86
92
90
80
94
92
87
97:3
94:6
92:8
95:5
>99:1
96:4
94:6
91:9
>99:1
>99:1
>99:1
84
47
33
69
86
75
66
35
88
90
92
CHiPr2
CHiPr2
CHiPr2
CHiPr2
CHiPr2
CHiPr2
Et
Rh2(S-TFPTTL)4 (3b)
Rh2(S-TCPTTL)4 (3c)
Rh2(S-TBPTTL)4 (3d)
Rh2(S-TBPTTL)4 (3d)
Rh2(S-TBPTTL)4 (3d)
Rh2(S-TBPTTL)4 (3d)
Rh2(S-TBPTTL)4 (3d)
Rh2(S-TBPTTL)4 (3d)
Rh2(S-TBPTTL)4 (3d)
9
tBu
10
tBu
11e
tBu
a
b
c
All reactions were carried out as follows: Rh(II) catalyst (1 mol %) was added to a solution of 4a (0.8 mmol, 4 equiv) and 5 (0.2 mmol) in CH2Cl2 (0.1 M).
Isolated yield.
Determined by 1H NMR spectroscopy of the crude reaction mixture.
Determined by HPLC analysis. See Supplementary data for details.
2 equiv of 4a was used.
d
e

4202
T. Goto et al. / Tetrahedron Letters 52 (2011) 4200–4203
Table 2
a
Enantio- and diastereoselective cyclopropanation of alkenes with tert-butyl
a-diazopropionate (5g) catalyzed by Rh2(S-TBPTTL)4
Rh2(S-TBPTTL)4
(3d) (1 mol %)
t
t
Me CO2 Bu
R1
R1
Me
CO2 Bu
+
N2
5g
CH2
Cl2, –78 °C
R2
R2
4 (2 equiv)
6
Entry
Alkenes
Time (h)
Cyclopropanes
trans:cisc
R1
R2
Yieldb (%)
eed (%)
1
2
3
4
5
6
7
8
4a
4b
4c
4d
4e
4f
4g
4h
4i
C6H5
4-CH3OC6H4
4-FC6H4
4-ClC6H4
4-CF3C6H4
1-Naphthyl
2-Naphthyl
(E)-C6H5CH@CH
nC4H9
H
H
H
H
H
H
H
H
8
9
10
10
9
12
12
12
24
12
9
6g
6h
6i
6j
6k
6l
6m
6n
6o
6p
6q
87
90
86
89
81
61
95
87
59
73
84
>99:1
>99:1
>99:1
>99:1
>99:1
98:2
>99:1
90:10
95:5
92
90
90
91
93
88
81
92
77
70
57
9e
10
11
H
CH3
C6H5
4j
4k
C6H5
C6H5
91:9
–
a
b
c
All reactions were carried out with 2 equiv of 4 on a 0.2 mmol scale unless otherwise stated.
Isolated yield.
Determined by 1H NMR spectroscopy of the crude reaction mixture.
Determined by HPLC analysis. See Supplementary data for details.
5 equiv of 4i was used.
d
e
than that observed with 2,4-dimethyl-3-pentyl ester 5f (88% ee,
entry 9). In a similar way to 6f, the absolute stereochemistry of
6g was determined to be 1R,2S (Scheme 2). When the reaction with
5g was conducted at ꢀ78 °C, the enantioselectivity was further en-
hanced to 90% ee without compromising the product yield or
greatly affecting the reaction rate (entry 10). In addition, virtually
the same result was obtained using only 2 equiv of styrene, in
which a slight increase in enantioselectivity was noted (92% ee, en-
try 11).
a 1,2-hydride shift or dimer products such as carbene dimer and
azine were observed. This protocol represents the first successful
example of a catalytic asymmetric cyclopropanation of alkenes
with
propanation methodology.27 Further extension of this method to
-diazobutanoates as well as stereochemical studies are currently
a-diazopropionates and partially complements the Fox cyclo-
a
underway.
Acknowledgments
Having determined the effectiveness of the combinational use
of Rh2(S-TBPTTL)4 as a catalyst and 5g as a carbene precursor, we
then explored the scope of the reaction with respect to the alkene
component (Table 2). Aside from essentially complete trans-diaste-
reoselectivity, high enantioselectivity was consistently observed
with styrenes bearing electron-donating or electron-withdrawing
substituents at the para position on the benzene ring (90–93% ee,
entries 2–5). The reaction with 1-vinylnaphthalene (4f) provided
exclusively the trans-cyclopropane product 6l with 88% ee, albeit
in moderate yield (61% yield, entry 6), while the use of 2-vinyl-
naphthalene (4g) gave 6m in excellent yield with a modest de-
crease in enantioselectivity (95% yield, 81% ee, entry 7). The
regioselective cyclopropanation of (E)-1-phenyl-1,3-butadiene
(4h) also proceeded cleanly and afforded predominantly the sty-
ryl-substituted trans-cyclopropane 6n in high yield with 92% ee
(entry 8). As might be expected from Davies’ studies on cycloprop-
anation chemoselectivity,33 the terminal aliphatic alkene 1-hexene
(4i) was found to be much less reactive, as the reaction with
5 equiv of 4i required a significantly longer reaction time (24 h)
to reach completion, with 6o being obtained in only 59% yield with
77% ee (entry 9). 1,1-Disubstituted alkenes 4j and 4k could be
cyclopropanated in good to high yields but with only modest
enantioselectivity (70% and 57% ee, entries 10 and 11).
This research was supported, in part, by a Grant-in Aid for Sci-
entific Research on Innovative Areas (Project No. 2105: Organic
Synthesis Based on Reaction Integration) from the Ministry of Edu-
cation, Culture, Sports, Science and Technology, Japan. We thank
Ms. S. Oka, and M. Kiuchi of the Center for Instrumental Analysis
at Hokkaido University for technical assistance in the MS and ele-
mental analyses.
Supplementary data
Supplementary data (detailed experimental procedures and full
spectroscopic characterization data for all new compounds) associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.tetlet.2011.06.008.
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dimethyl
phenyldiazoacetonitrile and
tetrakis[N-phthaloyl-(S)-1-adamantylglycinate], Rh2(S-PTAD)4, as
a
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1-aryl-2,2,2-trifluorodiazoetanes,
-diazoketones using dirhodium(II)
chiral
a
-
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a-nitro
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