RhII-catalyzed reaction of α-diazocarbonyl compounds bearing β-trichloroacetylamino substituent: C-H insertion versus 1,2-H shift

Article abstract of DOI:10.1002/asia.200900352

The Rh¹¹-carbene reaction is dramatically affected by the neighboring substituents. If the neighboring sub-stituent is an OH group, a1,2-H shift is the exclusive pathway. If it is an OAc group, a 1,2-acetoxy migration is observed. If it is p-to

Full text of DOI:10.1002/asia.200900352

FULL PAPERS
DOI: 10.1002/asia.200900352
RhII-Catalyzed Reaction of a-Diazocarbonyl Compounds Bearing b-
À
Trichloroacetylamino Substituent: C H Insertion versus 1,2-H Shift
Zhenhua Zhang,[a] Weifeng Shi,[a] Jian Zhang,[a] Bo Zhang,[a] Bingge Liu,[a] Yiyang Liu,[a]
Bo Fan,[a] Fengping Xiao,[a] Feng Xu,[a] and Jianbo Wang*[a, b]
Dedicated to the 100th anniversary of the College of Chemistry, Peking University
Abstract: The RhII-carbene reaction is
dramatically affected by the neighbor-
ing substituents. If the neighboring sub-
stituent is an OH group, a1,2-H shift is
the exclusive pathway. If it is an OAc
group, a 1,2-acetoxy migration is ob-
served. If it is p-toluenesulfonyl group,
substituent is a trichloroacetyl amino
sible for the switching of the RhII-car-
bene reaction pathway. The highly ste-
À
group, 1,5-C H insertion competes
II
À
with the 1,2-hydride shift, and no 1,3-
reoselective 1,5-C H insertions in Rh -
À
C H insertion can be observed. Both
catalyzed reaction of a-diazocarbonyl
compounds, bearing b-trichloroacetyla-
mino substituent, can be utilized as a
novel way to synthesize five-membered
cyclic b-amino acid derivatives.
electronic and steric factors are respon-
Keywords: carbenes
·
diazo
À
1,3 and 1,5-C H insertion are the
compounds · hydrides · insertion ·
substituent effects
major pathways, and the 1,2-H shift is
completely suppressed. If the adjacent
Introduction
tered (Scheme 1).[5–8] 1,2-H shift of carbene, which leads to
the formation of a carbon–carbon double bond, is a highly
feasible process.[5,6] The highly chemo- and stereoselective
1,2-H shift of RhII carbene is synthetically useful for con-
structing (Z)-b-unsaturated carbonyl compounds.[5]
II
À
Rh -mediated intramolecular C H insertion reaction repre-
sents a general approach for the construction of various car-
bocyclic compounds. In particular, 1,5-insertion is highly ef-
ficient and affords cyclopentane derivatives in high yields
with good regio- and stereoselectivity.[1,2] The usefulness of
RhII carbene 1,5-C H insertion has been well-demonstrated
À
by its applications in organic synthesis,[3] and it has also at-
À
tracted attentions recently as a unique way of C H bond ac-
tivation.[4] Although the insertion process is highly feasible,
it may suffer from other competing reaction pathways of
RhII carbene, among which 1,2-shift is commonly encoun-
[a] Z. Zhang, Dr. W. Shi, J. Zhang, B. Zhang, B. Liu, Y. Liu, B. Fan,
Dr. F. Xiao, Dr. F. Xu, Prof. Dr. J. Wang
Scheme 1. RhII carbene 1,5-C H insertion versus 1,2-H shift.
À
Beijing National Laboratory of Molecular Sciences (BNLMS)
Key Laboratory of Bioorganic Chemistry and Molecular Engineering
of Ministry of Education, College of Chemistry
Peking University, Beijing 100871 (P.R. China)
Fax : (+86)10-6275-7248
Investigations have revealed that the substituents adjacent
to the RhII-carbene center (X group in Scheme 1) have a
profound effect on the chemoselectivity of the RhII carbene.
If there is no substituent (X=H), 1,5-insertion is predomi-
nant [Eq. (1)]. A hydroxy substituent is found to promote a
1,2-H shift, and 1,5-insertion is completely shut down in
such a case [Eq. (2)].[6c] However, an acetoxy substituent
E-mail: wangjb@pku.edu.cn
[b] Prof. Dr. J. Wang
State Key Laboratory of Organometallic Chemistry
Chinese Academy of Sciences
Shanghai 200032 (P.R. China)
1112
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Chem. Asian J. 2010, 5, 1112 – 1119

leads to the migration of the acetoxy group itself, presuma-
bly through a 2,3-migration process [Eq. (3)].[8] It has been
II
À
reported that Rh -catalyzed 1,5-C H insertion can effective-
ly compete with the 1,2-H shift in some cases.[9] It is also
À
shown that the ratio of 1,5-C H insertion to 1,2-H shift is
significantly affected by the ligands on the RhII catalyst. Our
own study demonstrates that the substituents, such as NHTs,
Cl3C(O)NH, Ts, suppress the 1,2-H shift and result in the
formation of products that are formed through other group
[10]
À
migration or C H insertion.
In particular, we have ob-
À
served that intramolecular 1,5-C H insertion overrides the
1,2-H shift when the b substituent is a trichloroacetylamino
group [Eq. (4)].[10d] When the b substituent is a tosyl group,
À
both 1,3 and 1,5-C H insertions occur, but the 1,2-H shift is
Results and Discussion
completely suppressed [Eq. (5)].[10h] Systematic study reveals
that both electronic and steric effects are responsible for the
switch of 1,2-migratory aptitude of the RhII-carbene spe-
cies.[10c,g,k] In this paper, we report the details of the study on
the RhII-catalyzed reaction of diazo compounds, which bear
a b-trichloroacetylamino group.[11] This study reveals that
Nucleophilic addition of acyldiazomethane to aldehyde af-
fords b-hydroxy a-diazocarbonyl compounds, which can be
further derivatized. We have previously observed that the b
position of the a-diazocarbonyl compounds is liable to nu-
cleophilic substitution, which makes it possible to prepare a
series of diazo compounds with various substituents in the
adjacent position of the diazo group (Scheme 2).[10]
À
1,5-C H insertion can effectively compete with the 1,2-
H shift, which leads to the formation of five-membered
cyclic b-amino ester derivatives in a stereoselective manner.
Scheme 2. Nucleophilic substitution at the carbon adjacent to diazo
group.
The b-hydroxy a-diazo compounds 14a–j, which were
easily available through nucleophilic addition of acyldiazo-
methane with aldehyde,[12] were treated with Cl3CCN/NaH
under standard conditions for the imidation of alcohol
(Table 1).[13] The reaction proceeded through an unusual nu-
cleophilic substitution of the initially formed normal alcohol
imidation product by amide anion.
With diazo compounds 15a–j in hand, we next proceeded
to study their reaction with RhII catalysts. For the b-(tri-
chloroacetyl)amino a-diazocarbonyl compounds, we first ex-
amined the RhII-catalyzed reaction of 15a–e and the results
are summarized in Table 2. In the case of 15a and 15b, in
Abstract in Chinese:
À
which intramolecular C H insertion is not possible or not
À
competitive arising from the insertion into a primary C H
bond,[14] the Rh
(OAc)4-catalyzed reaction in CH2Cl2 at 08C
afforded only 1,2-H shift products 17a and 17b (Table 2, en-
tries 1, 2). For the diazo compound 15c, under the same
À
conditions, we obtained both 1,5-C H insertion and 1,2-
H shift products 16c and 17c in a ratio of 80:20 (entry 3).
The ratio was found to be slightly affected by the reaction
temperature: the high temperature favored the 1,2-H shift,
but the reaction at À208C became very sluggish, thus, it was
À
not possible to further increase the selectivity for 1,5-C H
insertion. We also examined two other typical RhII catalysts:
Rh2ACHTUNGTRNENUG(acam)4 and Rh2ACHTUNGTREN(NUGN O2CCF3)4, the former bears an elec-
Chem. Asian J. 2010, 5, 1112 – 1119
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1113

J. Wang et al.
FULL PAPERS
Table 1. Preparation of b-(trichloroacetyl)amino a-diazocarbonyl com- Table 3. Rh
pounds 15a–j.
2ACHTUNGTNER(NUNG OAc)4-catalyzed reaction of 15 f–j.
Entry
14a–j (R=)
t [h]
Yield [15,%][a]
Entry 16
17
16:17[a] Yield [%][b]
1
2
3
4
5
14a, CH3CH2
20
20
20
20
20
15a, 77
15b, 73
15c, 84
15d, 78
15e, 80
14b, CH
14c, CH
14d, CH
14e, CH
G
CHTUNGTRENNUNG
1
71:29
89:11
83
81
CHTUNGTRENNUNG
6
20
15 f, 79
2
3
7
24
15g, 92
88:12
88
8
23
15h, 88
9
20
24
15i, 90
15j, 74
4
5
85:15
0:100
81
10
89[c]
[a] Yield of isolated product after silica gel column chromatography.
[a] Ratio obtained from isolated products of 16 and 17. [b] Yield of isolated product
À
for 16 and 17 combined. [c] No C H insertion product was detected.
II
À
Table 2. Rh -catalyzed reaction of diazo compounds 15a–e: 1,5-C H in-
sertion versus 1,2-H shift.
tron-donating ligand whereas the latter bears an electron-
withdrawing ligand. It was observed that the reaction with
Rh
product was predominant (entry 6). Surprisingly, the Rh2
AHCTNUGTER(GNNNU O2CCF3)4-catalyzed reaction of 15c was exceptionally slow
2ACHTUNGTRENUN(NG acam)4 needed a high temperature, and the 1,2-H shift
and resulted in the recovery of the starting materials and a
complex mixture (entry 7). For the diazo substrates 15d and
15e, similar results were obtained (entries 8-15). Notably,
Entry 15
RhII
15a Rh2A(OAc)4
2A(OAc)4
2A(OAc)4
2A(OAc)4
2A(OAc)4
2A(acam)2
2A(O2CCF3)4 CH2Cl2
2A(OAc)4
2A(OAc)4
2A(acam)2
2A
2A(OAc)4
2A(OAc)4
2A(acam)4
2A
Solvent T [8C] 16:17[a] Yield [%][b]
1
G
CH2Cl2
CH2Cl2
CH2Cl2 30
CH2Cl2
0
0
0:100
0:100
80:20
72:28
–
68
73
89
74
with Rh2ACHTNUTRGENNG(U OAc)4 as catalyst in benzene at 808C, the reaction
2
3
4
5
6
7
8
9
10
11
12
13
14
15
15b Rh
15c Rh
15c Rh
15c Rh
15c Rh
15c Rh
15d Rh
15d Rh
15d Rh
15d Rh
15e Rh
15e Rh
15e Rh
15e Rh
CHTUNGTRENNUNG
À
N
gave essentially equal amounts of C H insertion products
and 1,2-H shift products (entries 9, 13).
N
0
[c]
R
CH2Cl2 À20
–
À
The structure of C H insertion product 16c (R’=CH3)
R
C6H6
80
0
29:71
–
80
[d]
was unambiguously confirmed by single-crystal X-ray analy-
sis, as shown in Figure 1.[15] The X-ray structure reveals that
the trichloroacetylamino group, the ester group, and the
R
–
E
CH2Cl2
C6H6
C6H6
0
88:12
50:50
29:71
–
89
87
80
N
80
80
0
N
methyl group are trans to one side. The Rh2ACTHUNTRGNE(UGN OAc)4-cata-
[d]
(O2CCF3)4 CH2Cl2
–
À
lyzed 1,5-C H insertion proceeded with high stereoselectiv-
ity, as only one diastereoisomer was observed. For the reac-
tion of 15d and 15e, we have also observed only one diaste-
N
CH2Cl2
C6H6
C6H6
0
84:16
50:50
40:60
–
94
99
98
G
80
80
0
N
[d]
(O2CCF3)4 CH2Cl2
–
À
reoisomer in each case for the C H insertion products. By
comparing the H NMR spectra of 16d and 16e with 16c,
[a] Product ratio was determined by 1H NMR (300 MHz) measurement
of the crude product. [b] Combined yield after column chromatography.
[c] The reaction with this substrate was exceptionally slow. About 50%
of diazo substrate was recovered after stirring at room temperature for 2
days in each case. [d] Starting material was recovered after stirring for
2 days.
1
we conclude that they all have the same all-trans configura-
tion.
The formation of 16c–e represents a new entry to the
five-membered cyclic b-amino acid derivatives, which have
1114
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Chem. Asian J. 2010, 5, 1112 – 1119

RhII-Catalyzed Reaction of a-Diazocarbonyl Compounds
Scheme 3. Transition states for RhII-catalyzed reaction of 15c–i.
products. The steric interactions between the ester group
and the R’ moiety in TS-B, and between the ester group and
the trichloroacetylamino group both in TS-C and TS-D, all
raise the energy in these transition states, resulting in the
predominant formation of product A.
Figure 1. X-ray structure of 16c.
attracted considerable attention recently.[16,17] To further
confirm the generality of this novel approach, the diazo sub-
strates 15 f–j were subjected to catalysis by Rh2ACTHNUTRGNEU(GN OAc)4. The
results are summarized in Table 3. Notably, in the case of
15 f, intramolecular cyclopropanation is also possible. How-
ever, no trace of such product can be detected (entry 1). An-
other special case is 15j, in which a carbon–carbon double
bond is present in the chain. Although the C=C bond has a
Conclusions
In summary, we have studied RhII-catalyzed reaction of b-
trichloroacetylamino-substituted
a-diazocarbonyl
com-
pounds. The b-substituent dramatically changes the reaction
pathway of the RhII carbene, and usually very facile 1,2-
À
H shift is suppressed and 1,5-C H insertion occurs predomi-
À
cis configuration, the expected 1,5-C H insertion product
nantly to afford the cyclic b-amino esters with high stereose-
lectivity. This may find application in organic synthesis as a
new entry to this type of b-amino acid derivatives. This
study further demonstrates the dramatic effect of neighbor-
ing groups on RhII-carbene reactions.
16j has not been detected (entry 5). This result further indi-
cates that conformational factors play dominant role in
RhII-carbene reactions.
À
The unusual preference of C H insertion over 1,2-H shift
in Rh
2A
no diazo compounds 15c–i may be interpreted from an elec-
tronic The electron-withdrawing
consideration.[14,18]
Experimental Section
NHCOCCl3 group will destabilize the transition state of the
1,2-H shift, in which positive charge develops at the carbon
from which the H migrates. This is consistent with our previ-
ous observation that 1,2-aryl, 1,2-vinyl, and 1,2-alkynyl mi-
grations occur exclusively in the presence of a b-hydrogen
when there is a b-trichloroacetylamino or b-tosylamino sub-
stituent present in the diazo substrate.[10]
General
All reactions were performed under a nitrogen atmosphere in a flame-
dried reaction flask, and the components were added using a syringe. All
solvents were distilled prior to use. The boiling point of petroleum ether
is between 30 and 608C. Benzene and toluene were distilled from sodium
prior to use. CH2Cl2 was distilled from CaH2. For chromatography, 200–
300 mesh silica gel (Qingdao, China) was employed. For the preparative
TLC, 10–40 mm silica gel GF254 (Qingdao, China) was used. Recrystalli-
zation was done using petroleum ether–ethyl acetate. 1H and 13C NMR
spectra were recorded at 200 MHz and 50 MHz with Varian Mercury 200
spectrometer, 300 MHz and 75 MHz with Varian Mercury 300 spectrome-
ter, or at 400 MHz and 100 MHz with a Bruker ARX 400 spectrometer.
Chemical shifts are reported in ppm using tetramethylsilane as internal
standard. IR spectra were recorded with a Nicolet 5MX-S infrared spec-
trometer. Mass spectra and HRMS were obtained on a VG ZAB-HS
mass spectrometer. Elemental analysis was conducted with a Vario EL
analyzer.
À
The high diastereoselectivity of the 1,5-C H insertion sug-
gests a very rigid transition state, and the all-trans selectivity
can be simply rationalized by the transition model that has
been suggested by Taber for Rh-mediated intramolecular
[18b]
À
1,5-C H insertion.
In Taberꢁs transition-state model, the
stereochemistry of the products is determined by the energy
differences between the chair-like transition states, in which
À
the C H bond being inserted, is parallel to the carbon–rho-
dium bond, while the energy differences are dependent on
steric and electronic factors within these structures. As de-
picted in Scheme 3, for the RhII-catalyzed reaction of 15c–i,
there are four chair-like diastereomeric transition states for
Syntheses
The preparation of b-hydroxy a-diazo carbonyl compounds 14a–j was
followed from the procedure in the literature.[12]
À
the 1,5-C H insertion, TS-A, TS-B, TS-C, and TS-D, in
which each leads to one of the four possible diastereomeric
Caution: Diazo compounds are generally toxic and potentially explosive.
They should be handled with care in a well-ventilated fumehood.
Chem. Asian J. 2010, 5, 1112 – 1119
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1115

J. Wang et al.
FULL PAPERS
(Z)-Ethyl 2-diazo-3-(hydroxyl)icos-11-enoate (14 f): Rf =0.33 (petroleum
1513, 1374, 823, 743 cmÀ1
;
1H NMR (200 MHz, CDCl3): d=1.01 (t, J=
ether: ethyl acetate=5:1); IR: n˜ =3454, 2925, 2094, 1695, 1466 cmÀ1
;
7.3 Hz, 3H), 1.31 (t, J=7.2 Hz, 3H), 1.50 (m, 2H), 1.97 (m, 2H), 4.26 (q,
J=7.2 Hz, 2H), 4.64 (dt, J=7.9, 7.8 Hz, 1H), 7.58 ppm (br, 1H);
13C NMR (50 MHz, CDCl3): d=13.45, 14.39, 19.43, 34.79, 49.16, 61.10,
92.35, 116.58, 161.41, 165.99 ppm; MS (EI): m/z (%): 301 (8) [(MÀ28)]+,
255 (42), 238 (24), 192 (43), 156 (58), 138 (100), 110 (12), 68 (12); ele-
mental analysis: calcd (%) for C10H14N3O3Cl3: C 36.33, H 4.27, N 12.71;
found: C 36.35, H 4.24, N 12.84.
1H NMR (300 MHz, CDCl3): d=0.88 (t, J=6.6 Hz, 3H), 1.26–1.76 (m,
27H), 2.02 (m, 4H), 2.95 (brs, 1H), 4.25 (q, J=7.2 Hz, 2H), 4.65 (m,
1H); 5.36 ppm (m, 2H); 13C NMR (75 MHz, CDCl3): d=14.06, 14.40,
22.64, 25.53, 27.12, 27.15, 29.13, 29.17, 29.26, 29.34, 29.47, 29.65, 29.71,
31.85, 32.56, 33.89, 60.92, 66.48, 129.68, 129.91, 166.64 ppm; MS (EI): m/z
(%): 352 (1.4) [(MÀ28)]+, 55 (100); elemental analysis: calcd (%) for
C22H40N2O3: C 69.43, H 10.59, N 7.36; found: C 69.68, H 10.90, N 7.01.
Ethyl 2-Diazo-3-(trichloroacetylamino)heptanoate (15c): Rf =0.55 (petro-
leum ether/ethyl acetate=10:1); IR: n˜ =3329, 2960, 2100, 1698, 1513,
Ethyl 2-diazo-3-hydroxy-6-methylheptanoate (14g): Rf =0.46 (petroleum
ether: ethyl acetate=5:1); IR: n˜ =3446, 2957, 2092, 1692, 1467, 746 cmÀ1
;
822, 744 cmÀ1 1H NMR (200 MHz, CDCl3): d=0.91 (t, J=6.9 Hz, 3H),
;
1H NMR (300 MHz, CDCl3). d=0.90 (d, J=6.6 Hz, 6H), 1.15–1.44 (m,
5H), 1.54–1.68 (m, 2H), 1.69–1.80 (m, 1H), 2.96 (brs, 1H), 4.25 (q, J=
7.2 Hz, 2H); 4.65 (m, H); 13C NMR (75 MHz, CDCl3): d=14.40, 22.40,
22.47, 27.73, 31.78, 34.55, 60.95, 66.79, 166.66 ppm; MS (EI): m/z (%):
186 (0.2) [(MÀ28)]+, 41 (100); elemental analysis: calcd (%) for
C10H18N2O3: C 56.06; H 8.47; N 13.07; found: C 56.18; H 8.66; N 13.16.
1.25 (m, 7H), 1.88 (m, 2H), 4.16 (q, J=7.2 Hz, 2H) 4.54 (dt, J=7.8
7.9 Hz, 1H), 7.47 ppm (brd, 1H); 13C NMR (50 MHz, CDCl3): d=13.77,
14.31, 21.91, 28.18, 32.45, 49.41, 61.08, 92.41, 161.49, 166.05 ppm; MS
(EI): m/z (%): decomposition; elemental analysis: calcd (%) for
C11H16N3O3Cl3: C 38.34, H 4.68, N 12.19; found: C 38.47, H 4.70, N 11.99.
Ethyl 2-Diazo-3-(trichloroacetylamino)nonanoate (15d): Rf =0.60 (petro-
leum ether/ethyl acetate=10:1); IR: n˜ =3333, 2931, 2100, 1698, 1512,
Ethyl 2-diazo-4-cyclohexyl-3-(hydroxy)butanoate (14h): Rf =0.40 (petro-
leum ether: ethyl acetate=5:1); IR: n˜ =3437, 2924, 2092, 1692, 1464,
1302, 822 cmÀ1 1H NMR (200 MHz, CDCl3): d=0.88 (t, J=6.3 Hz, 3H),
;
746 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=0.92 (m, 1H), 1.03–1.20 (m,
1.29 (m, 11H), 1.95 (m, 2H), 4.23 (q, J=7.3 Hz, 2H), 4.60 (dt, J=7.7,
8 Hz, 1H), 7.67 ppm (br, 1H); 13C NMR (50 MHz, CDCl3): d=13.83,
14.24, 22.31, 25.95, 28.44, 31.41, 32.41, 49.25, 60.99, 92.35, 161.46,
166.04 ppm; MS (EI): m/z (%): 343 (0.8) [(MÀ28)]+, 308 (13), 258 (42),
238 (14), 186 (11), 117 (13), 67 (19), 43 (52), 29 (100); elemental analysis:
calcd (%) for C13H20N3O3Cl3: C 41.90, H 5.41, N 11.28; found: C 42.01,
H 5.41, N 11.28.
2H), 1.29 (m, 4H), 1.37–1.50 (m, 2H), 1.60–1.81 (m, 6H), 2.91 (s, br,
1H), 4.25 (q, J=7.2 Hz, 2H), 4.81 ppm (m, 1H); 13C NMR (75 MHz,
CDCl3): d=14.40, 26.03, 26.11, 26.39, 32.72, 33.56, 33.89, 41.33, 60.92,
64.20, 166.63 ppm; MS (EI): m/z (%): 212 (0.7) [(MÀ28)]+, 55 (100); ele-
mental analysis: calcd (%) for C12H20N2O3: C 59.98, H 8.39, N 11.66;
found: C 59.90, H 8.56, N 11.42.
Ethyl 2-diazo-3-hydroxy-6-phenylhexanoate (14i): Rf =0.42 (petroleum
Ethyl 2-Diazo-3-(trichloroacetylamino)tetradecanoate (15e): Rf =0.67
(petroleum ether/ethyl acetate=10:1); IR: n˜ =3333, 2926, 2855, 2101,
ether: ethyl acetate=5:1); IR: n˜ =3444, 2982, 2092, 1689, 1294, 747 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=1.27 (t, J=7.2 Hz, 3H), 1.59–1.86 (m,
4H), 2.66 (t, J=7.2 Hz, 3H), 2.88 (br, 1H), 4.23 (q, J=7.2 Hz, 2H), 4.69
(t, J=7.2 Hz, 1H), 7.17–7.30 ppm (m, 5H); 13C NMR (75 MHz, CDCl3):
d=14.40, 27.32, 33.40, 35.31, 60.98, 66.37, 125.84, 128.32, 141.72,
166.55 ppm; MS (EI): m/z (%): 234 (0.2) [(MÀ28)]+, 91 (100); elemental
analysis: calcd (%) for C14H18N2O3: C 64.10, H 6.92, N 10.68; found:
C 64.03, H 6.95, N 10.69.
1698, 1512, 1374, 822 cmÀ1 1H NMR (200 MHz, CDCl3): d=0.88 (t, J=
;
6.3 Hz, 3H), 1.16–1.33 (m, 21H), 1.90 (m, 2H), 4.26 (q, J=7.3 Hz, 2H),
4.60 (dt, J=7.7, 7.8 Hz, 1H), 7.55 ppm (br, 1H); 13C NMR (50 MHz,
CDCl3): d=14.00, 14.31, 22.57, 26.06, 28.84, 29.21, 29.30, 29.36, 29.48,
31.80, 32.67, 49.41, 61.06, 92.42, 161.50, 166.09 ppm; MS (EI): m/z (%):
413 (2) [(MÀ28)+], 378 (39), 342 (11), 296 (15), 258 (35), 238 (65), 182
(25), 117 (11), 95 (27), 55 (51), 29 (100); elemental analysis: calcd (%)
for C18H30N3O3Cl3: C 48.82, H 6.83, N 9.49; found: C 48.99, H 7.02,
N 9.42.
(Z)-Ethyl 2-diazo-3-(hydroxy)dec-4-enoate (14j): Rf =0.45 (petroleum
ether: ethyl acetate=5:1); IR: n˜ =3461, 2957, 2094, 1693, 1286, 1105,
743 cmÀ1
;
1H NMR (300 MHz, CDCl3): d=0.88 (t, J=6.6 Hz, 3H), 1.27–
(Z)-Ethyl 2-diazo-3-(trichloroacetylamino)icos-11-enoate (15 f): Rf =0.40
(petroleum ether: ethyl acetate=15:1); IR: n˜ =3336, 2925, 2100, 1698,
1.44 (m, 9H), 2.08 (m, 2H), 3.24 (s, dr, H), 4.26 (q, J=7.2, 2H), 5.46–5.56
(m, 2H), 5.64 ppm (dt, J=7.5, 10.2 Hz, 1H); 13C NMR (75 MHz, CDCl3):
d=13.86, 14.33, 22.35, 27.90, 28.80, 31.25, 60.97, 63.27, 126.16, 134.34,
166.38 ppm; MS (EI): m/z (%): 212 (2.0) [(MÀ28)+], 29 (100); elemental
analysis: calcd (%) for C12H20N3O3: C 59.98, H 8.39, N 11.66; found:
C 60.15, H 8.27, N 11.61.
1511, 822 cmÀ1 1H NMR (300 MHz, CDCl3): d=0.88 (t, J=6.6 Hz, 3H),
;
1.26 (m, 25H), 1.86–2.02 (m, 6H), 4.25 (q, J=7.2 Hz, 2H), 4.60 (dt, J=
7.8, 7.8 Hz, 1H); 5.35 (m, 2H), 7.54 ppm (br, 1H); 13C NMR (75 MHz,
CDCl3): d=14.08, 14.35, 22.64, 26.09, 27.10, 27.16, 28.87, 29.05, 29.26,
29.46, 29.61, 29.70, 31.84, 32.56, 32.82, 49.43, 61.12, 92.37, 129.61, 129.97,
161.49, 166.13 ppm; MS (EI): m/z (%): 495 (0.8) [(MÀ28)+], 55 (100); el-
emental analysis: calcd (%) for C24H40Cl3N3O3: C 54.91, H 7.68, N 8.00;
found: C 55.03, H 7.73, N 7.89.
General Procedure for the Preparation of b-Trichloroacetylamino a-
Diazocarbonyl Compounds 15a–j
In a flamed three-necked round-bottom flask, b-hydroxy-a-diazo com-
pound (1.0 mmol) was dissolved in toluene (or benzene) (5 mL). Trichlor-
oacetonitrile (3.0 mmol, 98%) and sodium hydride (2.0 mmol, 60%)
were added to the solution at 08C. The mixture was stirred for 6 h be-
tween 08C and room temperature. The reaction was quenched with a sa-
turated solution of NaHCO3 at À308C, and then extracted with Et2O.
The combined organic layer was washed with brine, dried over anhydrous
MgSO4, and concentrated under reduced pressure with a rotavap. The
residue was subjected to silica gel column chromatography (petroleum
ether/Et2O=5:1) to afford the pure 15a–j.
Ethyl 2-diazo-3-trichloroacetylamino-6-methylheptanoate (15g): Rf =0.38
(petroleum ether/ethyl acetate=10:1); IR: n˜ =3332, 2958, 2100, 1697,
1511, 821 cmÀ1 1H NMR (300 MHz, CDCl3): d=0.89 (d, J=6.0 Hz, 6H),
;
1.29 (m, 5H), 1.59 (m, 1H), 1.91 (m, 2H), 4.26 (q, J=7.2 Hz, 2H), 4.57
(dt, J=7.8, 7.8 Hz, 1H); 7.53 ppm (br, 1H); 13C NMR (75 MHz, CDCl3):
d=14.36, 22.36, 22.48, 27.55, 30.78, 35.13, 49.70, 61.13, 92.37, 161.48,
166.10 ppm; MS (EI): m/z (%): 329 (0.1) [(MÀ28)+], 29 (100); elemental
analysis: calcd (%) for C12H18Cl3N3O3: C 40.19, H 5.06, N 11.72; found:
C 40.17, H 5.05, N 11.74.
Ethyl 2-diazo-4-cyclohexyl-3-(trichloroacetylamino)butanoate (15h): Rf =
0.41 (petroleum ether/ethyl acetate=15:1); IR: n˜ =3329, 2925, 2100,
Ethyl 2-Diazo-3-(trichloroacetylamino)pentanoate (15a): Rf =0.48 (pe-
troleum ether/ethyl acetate=10:1); IR: n˜ =3331, 2975, 2101, 1698, 1512,
1
1698, 1513, 823 cmÀ1; H NMR (300 MHz, CDCl3): d=0.93–1.04 (m, 2H),
822 cmÀ1
;
1H NMR (200 MHz, CDCl3): d=0.95 (t, J=7.5 Hz, 3H), 1.21
1.13–1.32 (m, 7H), 1.65–1.88 (m, 7H), 4.25 (q, J=7.2 Hz, 2H), 4.72 (dt,
J=7.8, 7.8 Hz, 1H), 7.45 ppm (br, 1H); 13C NMR (75 MHz, CDCl3): d=
14.38, 26.01, 26.28, 32.80, 32.95, 34.55, 40.15, 47.21, 61.13, 161.48,
166.12 ppm; MS (EI): m/z (%): 366 (0.4) [(MÀ28)]+, 55 (100); elemental
analysis: calcd (%) for C14H20Cl3N3O3: C 43.71, H 5.24, N 10.92; found:
C 43.88, H 5.40, N 10.80.
(t, J=7.1 Hz, 3H), 1.86 (m, 2H), 4.17 (q, J=7.1 Hz, 2H), 4.48 (dt, J=
7.8, 7.9 Hz, 1H), 7.61 ppm (d, br, 1H); 13C NMR (50 MHz, CDCl3): d=
10.51, 14.21, 25.74, 50.65, 60.99, 92.32, 161.50, 166.01 ppm; MS (EI): m/z
(%): 287 (3) [(MÀ28)]+, 258 (95), 230 (11), 194 (20), 124 (40); elemental
analysis: calcd (%) for C9H12N3O3Cl3: C 34.15, H 3.82, N 13.27; found:
C 34.09, H 3.83, N 13.44.
Ethyl 2-diazo-3-trichloroacetylamino-6-phenylhexanoate (15i): Rf =0.21
(petroleum ether/ethyl acetate=10:1); IR: n˜ =3330, 2981, 2099, 1696,
Ethyl 2-Diazo-3-(trichloroacetylamino)hexanoate (15b): Rf =0.35 (petro-
leum ether/ethyl acetate=10:1); IR: n˜ =3330, 2963, 2874, 2101, 1699,
1510, 1305, 821 cmÀ1 1H NMR (300 MHz, CDCl3): d=1.26 (t, J=7.2 Hz,
;
1116
www.chemasianj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 1112 – 1119

RhII-Catalyzed Reaction of a-Diazocarbonyl Compounds
3H), 1.73 (m, 2H), 1.86–2.03 (m, 2H), 2.66 (t, J=7.2 Hz, 2H), 4.21 (q,
J=7.2 Hz, 2H), 4.63 (dt, J=7.5, 7.5 Hz, 1H), 7.15–7.31 (m, 5H),
7.65 ppm (dr, 1H); 13C NMR (75 MHz, CDCl3): d=14.24, 27.77, 32.03,
34.93, 49.12, 61.07, 92.28, 125.92, 128.18, 128.33, 141.18, 161.51,
166.01 ppm; MS (EI): m/z (%): 377 (0.3) [(MÀ28)]+, 104 (100); elemen-
tal analysis: calcd (%) for C16H18Cl3N3O3: C 47.25, H 4.46, N 10.33;
found: C 46.93, H 4.47, N 10.19.
r1, trans-2, trans-5, Ethyl 2-Trichloroacetylamino-5,5-dimethylcyclopenta-
necarboxylate (16g): Rf =0.18 (petroleum ether: ethyl acetate=15:1);
IR: n˜ =3330, 2938, 1708, 1640, 1211, 872 cmÀ1 1H NMR (400 MHz,
;
CDCl3): d=0.95 (s, 3H), 1.24 (s, 3H), 1.28 (t, J=7.2 Hz, 3H), 1.59–1.83
(m, 3H), 2.23–2.32 (m, 1H), 2.64 (d, J=9.0 Hz, 1H), 4.19 (m, 2H), 4.57
(m, 1H), 6.87 ppm (brd, J=5.1 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d=14.20, 24.14, 29.09, 29.48, 39.76, 41.98, 55.02, 59.71, 60.494, 92.53,
161.20, 171.96 ppm; MS (EI): m/z (%): 331 (0.1) [(M+2)]+, 329 (0.1)
(M+), 95 (100); HRMS: m/z (%) calcd for C12H18Cl3NO3: 329.0352;
found: 329.0338.
(Z)-Ethyl 2-diazo-3-(trichloroacetylamino)dec-4-enoate (15j): Rf =0.45
(petroleum ether/ethyl acetate=10:1); IR: n˜ =3328, 2959, 2102, 1697,
1509, 1238, 821 cmÀ1 1H NMR (300 MHz, CDCl3): d=0.89 (t, J=6.6 Hz,
;
3H), 1.27–1.44 (m, 9H), 2.14 (dt, J=6.3, 6.3 Hz, 2H), 4.26 (q, J=7.2,
2H), 5.44 (dd, J=7.2, 7.2 Hz, 1H), 5.66–5.71 (m, 2H), 7.54 ppm ( br,
1H); 13C NMR (75 MHz, CDCl3): d=13.92, 14.36, 22.41, 27.77, 28.85,
31.28, 46.33, 61.20, 92.28, 123.62, 135.51, 161.24, 165.84 ppm; MS (EI): m/
z (%): 355 (2.0) [(MÀ28)]+, 29 (100); elemental analysis: calcd (%) for
C14H20Cl3N3O3: C 43.71, H 5.24, N 10.92; found: C 43.62; H 5.25; N 10.76.
r1, trans-2, trans-3a, trans-7a, Ethyl 2-Trichloroacetylamino-octahydro-
1H-indene-1-carboxylate (16h): Rf =0.15 (petroleum ether: ethyl ace-
tate=15:1); IR: n˜ =3333, 2926, 1694, 1522, 1259, 821 cmÀ1 1H NMR
;
(400 MHz, CDCl3): d=1.07–1.29 (m, 7H), 1.43 (m, 1H), 1.58 (m, 1H),
1.77–1.97 (m, 6H), 2.41 (dd, J=7.4, 11.1 Hz 1H), 4.19 (q, J=7.2 Hz,
2H), 4.46 (m, 2H), 6.94 ppm (d, br, J=5.9 Hz, 1H); 13C NMR (100 MHz,
CDCl3): d=14.12, 25.51, 25.65, 29.99, 30.99, 37.86, 44.43, 49.44, 54.42,
56.70, 60.66, 92.42, 161.19, 173.46 ppm; MS (EI): m/z (%): 331 (0.1)
[(M+2)]+, 329 (0.1) (M+), 95 (100). HRMS: m/z (%) calcd for
C14H20Cl3NO3: 355.0509; found: 355.0495.
General Procedure for Rh
(OAc)4-Catalyzed Reaction of 15a–j
2A(OAc)4 (1 mol%) was dissolved in
In a flamed round-bottom flask, Rh CTHNUGTRENNUNG
anhydrous CH2Cl2 (10 mL). A solution of diazo substrate 15a–j in anhy-
drous CH2Cl2 was added dropwise at 08C for 15 min. After stirred for an-
other 60 min, the solution was concentrated under reduced pressure, and
the residue was subjected to flash silica gel chromatography to afford the
products.
r1, trans-2, trans-5, Ethyl 2-Trichloroacetylamino-5-phenylcyclopentane-
carboxylate (16i): Rf =0.19 (petroleum ether: ethyl acetate=15: 1); IR:
n˜ =3335, 2975, 1694, 1523, 1186, 821 cmÀ1 1H NMR (400 MHz, CDCl3):
;
d=1.49 (t, J=7.2 Hz 3H), 1.88–2.03 (m, 2H), 2.22–2.27 (m, 1H), 2.39–
2.44 (m, 1H), 2.93 (t, J=10.0 Hz 1H), 3.49 (dt, J=9.5, 9.5 Hz 1H), 4.09
(q, J=7.2 Hz, 2H), 4.47 (m, 1H), 7.01 (d, br, J=6.7 Hz, 1H), 7.20–
7.32 ppm (m, 5H); 13C NMR (100 MHz, CDCl3): d=13.98, 31.20, 31.52,
47.47, 56.54, 57.58, 60.97, 92.38, 126.74, 126.96, 128.54, 142.16, 161.42,
172.62 ppm; MS (EI): m/z (%): 379 (7.0) [(M+2)]+, 377 (7.0) (M+), 268
(100); HRMS: m/z (%) calcd for C16H18Cl3NO3: 377.0352; found:
377.0360.
r1, trans-2, trans-5, Ethyl 2-Trichloroacetylamino-5-methyl-cyclopentane-
carboxylate (16c): Rf =0.31 (petroleum ether: ethyl acetate=10:1); IR:
n˜ =3334, 2960, 1701, 1524, 1198, 827 cmÀ1 1H NMR (300 MHz, CDCl3):
;
d=1.11 (d, J=7.8 Hz, 3H), 1.26 (t, J=7.2 Hz, 3H), 1.45 (m, 1H), 1.67
(m, 1H), 1.98 (m, 1H), 2.25 (m, 3H), 4.18 (q, J=7.2 Hz, 2H), 4.37 (m,
1H), 6.29 ppm (br, 1H); 13C NMR (75 MHz, CDCl3): d=14.18, 19.52,
31.00, 31.60, 37.42, 56.47, 58.01, 60.91, 92.48, 161.32, 173.19 ppm; MS
(EI): m/z (%): 316 (0.25) [(M+1)]+, 280 (37), 206 (23), 198 (17), 152
(49), 115 (95), 109 (71), 81 (100), 29 (38); elemental analysis: calcd (%)
for C11H16NO3Cl3: C 41.73, H 5.09, N 4.42, found: C 41.94, H 5.16, N 4.36.
(E)-Ethyl 3-Trichloroacetylamino-2-pentenoate (17a): Rf =0.57 (petrole-
um ether/ethyl acetate=10:1); IR: n˜ =3332, 2981, 1712, 1520, 1201, 1142,
820, 673 cmÀ1 1H NMR (200 MHz, CDCl3): d=1.10 (t, J=7.8 Hz, 3H),
;
1.30 (t, J=7.0 Hz, 3H), 2.90 (q, J=7.6 Hz, 2H), 4.20 (q, J=7.0 Hz, 2H),
6.74 (s, 1H), 7.79 ppm (s, 1H); 13C NMR (50 MHz, CDCl3): d=12.38,
14.17, 24.84, 59.94, 105.46, 151.57,154.97, 159.10, 166.73 ppm; MS (EI): m/
z (%) 287 (4) (M+), 252 (6), 241 (24), 213 (9), 206 (25), 178 (17), 142
(56), 124 (100); elemental analysis: calcd (%) for C9H12NO3Cl3: C 37.46,
H 4.19, N 4.85; found: C 37.66, H 4.37, N 4.65.
r1, trans-2, trans-5, Ethyl 2-Trichloroacetylamino-5-propyl-cyclopentane-
carboxylate (16d): Rf =0.37 (petroleum ether: ethyl acetate=10:1); IR:
n˜ =3334, 2960, 1701, 1525, 828 cmÀ1 1H NMR (200 MHz, CDCl3): d=
;
0.90 (t, J=6.7 Hz, 3H), 1.16~1.50 (m, 8H), 1.68 (m, 1H), 2.04 (m, 1H),
2.20~2.42 (m, 3H), 4.16 (q, J=7.3 Hz, 2H), 4.36 (m, 1H), 6.86 ppm (br,
1H); 13C NMR (50 MHz, CDCl3): d=14.03, 14.09, 20.79, 29.20, 30.99,
37.47, 41.93, 56.54, 56.65, 60.83, 92.44, 161.28, 173.53 ppm; MS (EI): m/z
(%): 344 (0.2) [(M+1)]+, 343 (0.08) (M+), 308 (40), 234 (23), 180 (34),
143 (100), 137 (43), 109 (53), 67 (45), 55 (14), 29 (37); elemental analysis:
calcd (%) for C13H20NO3Cl3 : C 45.30, H 5.85, N 4.06; found: C 45.43,
H 5.90, N 3.98.
(E)-Ethyl 3-Trichloroacetylamino-2-hexenoate (17b): Rf =0.48 (petrole-
um ether/ethyl acetate=10:1); IR: n˜ =3334, 2967, 1711, 1520, 1143,
821 cmÀ1 1H NMR (200 MHz, CDCl3): d=0.98 (t, J=7.5 Hz, 3H), 1.28
;
(t, J=7.2 Hz, 3H), 1.65 (m, 2H), 2.86 (t, J=7.7 Hz, 2H), 4.18 (q, J=
7.2 Hz, 2H), 6.77 (s, 1H), 7.78 ppm (s, 1H); 13C NMR (50 MHz, CDCl3):
d=13.50, 14.18, 21.44, 33.11, 59.91, 92.20, 106.07, 150.29, 158.99,
166.82 ppm; MS (EI): m/z (%): 301 (5) (M+), 266 (31), 257 (41), 220
(68), 192 (65), 138 (69), 110 (16), 95 (11), 55 (16), 29 (100); elemental
analysis: calcd (%) for C10H14NO3Cl3 : C 39.69, H 4.66, N 4.63; found:
C 39.78, H 4.71, N 4.74.
r1, trans-2, trans-5, Ethyl 2-Trichloroacetylamino-5-octylcyclo-pentane-
carboxylate (16e): Rf =0.43 (petroleum ether: ethyl acetate=10:1); IR:
n˜ =3334, 2926, 1697, 1525, 822 cmÀ1 1H NMR (200 MHz, CDCl3): d=
;
0.88 (t, J=6.7 Hz, 3H), 1.16–1.29 (m, 16H), 1.38~1.77 (m, 3H), 1.90–
2.07 (m, 1H), 2.16–2.41 (m, 3H), 4.17 (q, J=7.2 Hz, 2H), 4.35 (m, 1H),
6.84 ppm (d, 1H); 13C NMR (50 MHz, CDCl3): d=14.00, 14.10, 22.56,
27.61, 29.16, 29.25, 29.40, 29.55, 31.01, 31.77, 35.24, 42.19, 56.58, 56.70,
60.83, 92.49, 161.28, 173.53 ppm; MS (EI): m/z (%): 414 (0.43) [(M+1)]+,
378 (64), 304 (23), 250 (26), 213 (100), 185 (28), 121 (7), 81 (29), 67 (56),
(E)-Ethyl 3-Trichloroacetylamino-2-nonenoate (17d): Rf =0.54 (petrole-
um ether: ethyl acetate=10:1); IR: n˜ =3334, 2930, 1713, 1519, 1141, 819,
672 cmÀ1 1H NMR (300 MHz, CDCl3): d=0.88 (t, J=6.6 Hz, 3H), 1.26–
;
1.39 (m, 9H), 1.58 (m, 2H), 2.87 (t, J=7.8 Hz, 2H), 4.19 (q, J=7.2 Hz,
2H), 6.77 (s, 1H), 7.74 ppm (s, 1H); 13C NMR (75 MHz, CDCl3): d=
13.98, 14.23, 22.48, 28.09, 28.80, 29.66, 31.45, 59.96, 92.45, 105.88, 150.50,
158.98, 166.86 ppm; MS (EI): m/z (%): 343 (1) (M+), 308 (21), 238 (62),
198 (26), 180 (26), 109 (16), 57 (25), 43 (56), 29 (100).
29 (62); elemental analysis: calcd (%) for C18H30NO3Cl3
H 7.29, N 3.38; found: C 52.23, H 7.44, N 3.12.
: C 52.12,
r1, trans-2, trans-5, Ethyl 2-Trichloroacetylamino-5-((Z)-tridec-4-enyl)
cyclopentanecarboxylate (16 f): Rf =0.55 (petroleum ether/ethyl acetate=
10:1); IR: n˜ =3329, 2923, 1733, 1524, 836 cmÀ1 1H NMR (400 MHz,
;
(E)-Ethyl 3-Trichloroacetylamino-2-tetradecenoate (17e): Rf =0.56 (pe-
troleum ether/ethyl acetate=10:1); IR: n˜ =3335, 2926, 2855, 1713, 1519,
CDCl3): d=0.89 (t, J=6.6 Hz, 3H), 1.25–1.71 (m, 23H), 1.99 (m, 5H),
2.26 (m, 2H), 2.37 (m, 1H), 4.17 (q, J=7.2 Hz, 2H), 4.35 (m, 1H), 5.35
(m, 2H), 6.83 ppm (d, br, J=5.6 Hz, 1H); 13C NMR (100 MHz, CDCl3):
d=14.08, 14.16, 22.64, 27.02, 27.18, 27.32, 29.27, 29.60, 29.65, 29.68, 29.71,
31.04, 31.86, 35.18, 42.17, 56.59, 56.72, 60.90, 92.50, 129.38, 130.12, 161.33,
173.53 ppm; MS (EI): m/z (%): 497 (0.7) [(M+2)]+, 495 (0.6) (M+), 287
(100); HRMS: m/z (%) calcd for C24H40Cl3NO3: 495.2074; found:
495.2047.
1139, 795 cmÀ1 1H NMR (300 MHz, CDCl3): d=0.88 (t, J=6.6 Hz, 3H),
;
1.26–1.31 (m, 19H), 1.53~1.62 (m, 2H), 2.87 (t, J=7.7 Hz, 2H), 4.17 (q,
J=7.0 Hz, 2H), 6.77 (s, 1H), 7.73 ppm (s, 1H); 13C NMR (75 MHz,
CDCl3): d=14.09, 14.24, 22.65, 28.13, 29.13, 29.31, 29.45, 29.56, 31.42,
31.87, 59.55, 92.47, 105.89, 150.50, 158.96, 166.86 ppm; MS (EI): m/z (%):
413 (1) (M+), 378 (34), 342 (12), 268 (27), 238 (80), 150 (21), 95 (16), 55
(54), 43 (98), 29 (100).
Chem. Asian J. 2010, 5, 1112 – 1119
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
1117

J. Wang et al.
FULL PAPERS
(2E, 11Z)-Ethyl 3-Trichloroacetylaminoicosa-2,11-dienoate (17 f): Rf =
0.64 (petroleum ether/ethyl acetate=10:1); IR: n˜ =3341, 2926, 1737,
G. J. Fan, Tetrahedron: Asymmetry 2006, 17, 297–307; b) G. J. Fan,
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1518, 1197, 886 cmÀ1 1H NMR (300 MHz, CDCl3): d=0.88 (t, J=6.6 Hz,
;
3H), 1.26–1.60 (m, 25H), 2.00 (m, 4H), 2.87 (t, J=7.8 Hz, 2H), 4.17 (q,
J=7.2 Hz, 2H), 5.34 (m, 2H), 6.67 (s, 1H), 7.74 ppm (s, 1H); 13C NMR
(75 MHz, CDCl3): d=14.09, 14.22, 22.64, 27.12, 27.18, 28.11, 29.08, 29.19,
29.28, 29.48, 29.62, 29.71, 31.39, 31.86, 32.56, 59.93, 92.44, 105.85, 129.63,
129.98, 150.49, 158.95, 166.82 ppm; MS (EI): m/z (%): 497 (0.8)
[(M+2)]+, 495 (0.8) (M+), 29
ACTHNUTRGNE(NUG 100); HRMS: m/z (%) calcd for
C24H40Cl3NO3: 495.2074; found: 495.2070.
(E)-Ethyl 3-Trichloroacetylamino-6-methyl-2-heptenoate (17g); Rf =0.32
(petroleum ether/ethyl acetate=15:1); IR: n˜ =3335, 2940, 1710, 1646,
[3] For recent examples of RhII carbene C H insertion in natural prod-
À
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9628; f) S. P. Chavan, M. Thakkar, R. K. Kharul, A. B. Pathak, G. V.
Bhosekar, M. M. Bhadbhade, Tetrahedron 2005, 61, 3873–3879;
g) D. F. Taber, K. J. Frankowski, J. Org. Chem. 2005, 70, 6417–6421;
h) U. K. Tambar, D. C. Ebner, B. M. Stoltz, J. Am. Chem. Soc. 2006,
128, 11752–11753.
1
1518, 1203, 870 cmÀ1; H NMR (300 MHz, CDCl3): d=0.96 (d, J=6.6 Hz,
6H), 1.28 (t, J=7.2 Hz, 3H), 1.48 (m, 2H), 1.66 (m, 1H), 2.88 (t, J=
8.1 Hz, 2H), 4.17 (q, J=7.2 Hz, 2H), 6.74 (s, 1H), 7.74 ppm (s, 1H);
13C NMR (75 MHz, CDCl3): d=14.24, 22.50, 27.92, 29.44, 37.00, 59.96,
92.42, 105.76, 150.80, 158.97, 166.81 ppm; MS (EI): m/z (%): 331 (1.4)
[(M+2)]+, 329 (1.5) (M+), 29 (100); HRMS: m/z (%) calcd for
C12H18Cl3NO3: 329.0352; found: 329.0347.
(E)-Ethyl 3-Trichloroacetylamino-4-cyclohexyl-2-butenoate (17h): Rf =
0.33 (petroleum ether/ethyl acetate=15: 1); IR: n˜ =3337, 2925, 1712,
1
1518, 1143, 818 cmÀ1; H NMR (300 MHz, CDCl3): d=1.03–1.31 (m, 8H),
1.56–1.78 (m, 6H), 2.77 (d, J=7.5 Hz, 2H), 4.17 (q, J=7.2 Hz, 2H), 6.86
(s, 1H), 7.71 ppm (s, 1H); 13C NMR (75 MHz, CDCl3): d=14.22, 26.03,
29.65, 32.75, 32.98, 37.35, 38.88, 59.92, 92.44, 106.58, 149.23, 158.76,
166.97 ppm; MS (EI): m/z (%): 357 (1.5) [(M+2)]+, 355 (1.5) (M+), 55
(100); HRMS: m/z (%) calcd for C14H20Cl3NO3: 355.0509; found:
355.0503.
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Lett. 1983, 24, 5355–5358; d) T. Hudlicky, H. F. Olivo, M. G.
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Am. Chem. Soc. 2002, 124, 12426–12427.
(E)-Ethyl 3-Trichloroacetylamino-6-phenyl-2-hexenoate (17i): Rf =0.28
(petroleum ether/ethyl acetate=15: 1); IR: n˜ =3317, 2962, 1708, 1533,
1146, 826 cmÀ1 1H NMR (300 MHz, CDCl3): d=1.28 (t, J=7.2 Hz, 3H),
;
1.92 (tt, J=7.2, 7.5 Hz, 2H), 2.72 (t, J=7.2 Hz, 2H), 2.90 (t, J=7.5 Hz,
2H), 4.17 (q, J=7.2 Hz, 2H), 6. 77ACHTNUTRGNE(UNG s, 1H), 7.18–7.31 (m, 5H), 7.64 ppm
(s, 1H); 13C NMR (75 MHz, CDCl3): d=14.23, 29.70, 31.02, 35.13, 60.03,
92.32, 106.21, 126.12, 128.32, 128.49, 141.17, 150.03, 159.02, 166.81 ppm;
MS (EI): m/z (%): 379 (0.3) [(M+2)]+, 377 (0.3) (M+), 104 (100);
HRMS: m/z (%) calcd for C16H18Cl3NO3: 377.0352; found: 377.0360.
[7] 1,2-Alkyl or 1,2-aryl migration, see:a) K. Nagao, M. Chiba, S. W.
Kim, Synthesis 1983, 197–199; b) A. Padwa, S. F. Hornbuckle, Z.
Zhang, L. Zhi, J. Org. Chem. 1990, 55, 5297–5299; c) T. Ye, M. A.
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e) M. Vitale, T. Lecourt, C. G. Sheldon, V. K. Aggarwal, J. Am.
Chem. Soc. 2006, 128, 2524–2525; f) S. Chen, Y. Zhao, J. Wang, Syn-
thesis 2006, 1705–1710; g) H. Xu, W. Zhang, D. Shu, J. B. Werness,
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Ed. 2008, 47, 8933–8936.
ACHTUNGTRENNUNG
;
3H), 1.23–1.45 (m, 9H), 1.94 (dt, J=6.9, 6.9 Hz, 2H), 4.26 (q, J=7.2,
2H), 5.86–6.01 (m, 2H), 7.90 (d, J=11.4 Hz, 1H), 8.36 ppm ( d, J=
11.1 Hz, 1H); 13C NMR (100 MHz, CDCl3): d=13.91, 14.24, 22.31, 28.58,
29.13, 31.16, 60.91, 91.54, 115.10, 119.89, 130.40, 137.41, 159.06,
165.86 ppm; MS (EI): m/z (%): 357 (9.9) [(M+2)]+, 355 (10.0) (M+), 320
(100); elemental analysis: calcd (%) for C14H20Cl3NO3: C 47.14, H 5.65,
N 3.93; found: C 47.17, H 5.58, N 3.98.
[8] 1,2-Acetoxy migration, see: a) F. J. Lꢂpez-Herrera, F. Sarabia-
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436–441.
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The project is generously supported by NSFC (Grant No. 20832002,
20772003, 20821062), the Ministry of Education of China, and National
Basic Research Program of China (973 Program, No. 2009CB825300).
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1118
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ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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RhII-Catalyzed Reaction of a-Diazocarbonyl Compounds
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Received: August 7, 2009
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Published online: December 10, 2009
Chem. Asian J. 2010, 5, 1112 – 1119
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemasianj.org
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