An atom-economic synthesis of bicyclo[3.1.0]hexanes by rhodium N-heterocyclic carbene-catalyzed diastereoselective tandem hetero-[5 + 2] cycloaddition/claisen rearrangement reaction of vinylic oxiranes with alkynes

Article abstract of DOI:10.1021/ja2014604

The first synthetic application of a vinylic oxirane as a heteroatom-containing five-atom component in transition-metal-catalyzed cycloaddition reactions is reported. A new, efficient, diastereoselective tandem intramolecular hetero-[5 + 2] cycloaddition/Claisen rearrangement of vinylic oxirane-alkyne substrates that uses a rhodium NHC complex and provides strategically novel, atom-economic, regiospecific, and diastereoselective access to [3.1.0] bicyclic products has been developed.

Full text of DOI:10.1021/ja2014604

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pubs.acs.org/JACS
An Atom-Economic Synthesis of Bicyclo[3.1.0]hexanes by Rhodium
N-Heterocyclic Carbene-Catalyzed Diastereoselective Tandem
Hetero-[5 þ 2] Cycloaddition/Claisen Rearrangement Reaction
of Vinylic Oxiranes with Alkynes
Jian-Jun Feng and Junliang Zhang*
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University,
3663 North Zhongshan Road, Shanghai 200062, P. R. China
S Supporting Information
b
During the course of our ongoing development of rhodium-
catalyzed cyclization17aꢀe and oxirane chemistry,17f,g we became
ABSTRACT: The first synthetic application of a vinylic
oxirane as a heteroatom-containing five-atom component in
transition-metal-catalyzed cycloaddition reactions is report-
ed. A new, efficient, diastereoselective tandem intramole-
cular hetero-[5 þ 2] cycloaddition/Claisen rearrangement
of vinylic oxirane-alkyne substrates that uses a rhodium
NHC complex and provides strategically novel, atom-eco-
nomic, regiospecific, and diastereoselective access to [3.1.0]
bicyclic products has been developed.
interested in whether vinylic oxiranes could be used asheteroatom-
containing five-atom components in metal-catalyzed intramolecu-
lar hetero-[5 þ 2] cycloadditions via CꢀO bond cleavage of the
epoxide motif to afford the 2,5-dihydrooxepin (Scheme 1). The
2,5-dihydrooxepin would then readily undergo a subsequent
Claisen rearrangement,18 providing a strategically novel, atom-
economic route to [3.1.0] bicycles, which are widely found in
natural products19a and pharmaceutical agents.19b,c Among those
methods for synthesizing bicyclo[3.1.0]hexanes, the most com-
mon and well-known process is intramolecular cyclopropanation
of suitably functionalized substrates, including transition-metal-
catalyzed decomposition of diazo compounds followed by intra-
molecularalkeneinsertion,20 organocatalytic Michael-initiatedring
closure,21 intramolecular Simmons-Smith cyclopropanation,22 cy-
clization of lithiated epoxides,23 and others.24 However, atom-
economic methods for the synthesis of these compounds are
relatively rare, except for transition-metal-catalyzed cycloisomeri-
zation of enynes.25 Herein we report the first Rh N-heterocyclic
carbene (NHC)-catalyzed tandem intramolecular hetero-
[5 þ 2] cycloaddition/Claisen rearrangement reaction of vinylic
oxiraneꢀalkyne substrates, which provides practical, regiospeci-
fic, and diastereoselective access to bicyclo[3.1.0]hexanes. To the
best of our knowledge, this is the first example of the use of vinylic
oxiranes as a heteroatom-containing five-atom component in
transition-metal-catalyzed cycloadditions.
We began to examine this hypothesis by subjecting substrate
1a to a solution of various rhodium catalysts (Table 1). To our
surprise, the reaction did not occur when [Rh(CO)2Cl]22a,bor
(PPh3)3RhCl/AgSbF62c,d was used as the catalyst, even though
these are commonly used in intramolecular [5 þ 2] cycloaddi-
tions (entries 2 and 3). No reaction occurred in the absence of
rhodium catalyst (entry 1). With 5 mol % [Rh(COD)Cl]2/
AgSbF6 in 1,2-dichloroethane (DCE) at room temperature, a
mixture of 2a and some unidentified aldehydes was obtained
(entry 4). Increasing the temperature to 75 °C did not improve
the yield (entry 5). When used alone, [Rh(COD)Cl]2 failed to
catalyze this reaction (entry 6). On the other hand, use of AgSbF6
alone induced isomerization of the epoxide to the aldehyde
derivatives (entry 7). Hence, we carried out this reaction in the
ransition-metal-catalyzed cycloaddition reactions have pro-
T
ven reliable for the construction of polycyclic carbocycles
and heterocycles.1 Many impressive examples in the area of
polycyclic carbocycle synthesis have emerged. For example, the
research groups of Wender,2 Trost,3 and Yu4 have done seminal
work on the cycloadditions of vinylcyclopropanes (VCPs) and π
systems. Alternatively, the [4 þ 3] cycloaddition of allyl cations
and dienes is an efficient method for making seven-membered
rings.5 Lautens,6 Motherwell,7 Nakamura,8 and Mascare~nas9
have developed intramolecular [3 þ 2] cycloadditions of methyl-
enecyclopropanes (MCPs) with various unsaturated com-
pounds for the synthesis of five-membered rings. Evans has
described the merit of the rhodium-catalyzed [2 þ 2 þ 2] and
[4 þ 2 þ 2] reactions of 1,6-enynes with alkynes and 1,3-
butadienes.10 Recently, Tanaka has demonstrated an elegant
system for enantioselective [2 þ 2 þ 2] cycloadditions.11 On the
other hand, the formation of polycyclic heterocycles by these
processes has focused mainly on using carbonyl compounds,12aꢀd
1-azadienes,12e azomethine imines,12f nitrones,12gꢀj isocyanates,12k,l
etc.,1e as heteroatom components.
Vinylic oxiranes are easily made, versatile synthons13 that are
commonly used as substrates in metal-catalyzed substitution
reactions,14 rearrangements,15 and [3 þ 2] cycloadditions.16
However, there has been no report on the utilization of vinyl
oxiranes as a heteroatom-containing five-atom partner in cy-
cloaddition reactions. If this approach is successful, it will give
new insight into the synthetic application of vinylic oxiranes, but
it faces many obstacles and challenges, considering that epoxides
activated by an adjacent aryl or vinyl substituent easily undergo
isomerization to carbonyl compounds in the presence of comp-
lexes of metals such as Rh,15aꢀc Ru,15d Pd,15eꢀj etc.15k,l
Received: February 16, 2011
Published: April 27, 2011
r
2011 American Chemical Society
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COMMUNICATION
Scheme 1
Table 2. Rh(NHC)-Catalyzed Tandem Intramolecular Het-
ero-[5 þ 2] Cycloaddition/Claisen Rearrangement Reactiona
product
(% yieldb)
entry
X
R1/R2/R3 (1)
time (h)
1
2
C(CO2Me)2
C(CO2Me)2
Ph/Ph/H (1a)
4-MeOC6H4/
Ph/H (1b)
2
5
2a (92)
2b (91)
2c (55)
3
C(CO2Me)2
4-NO2C6H4/
Ph/H (1c)
8
Table 1. Optimization of Reaction Conditionsa
4
5c
6e
7
C(CO2Me)2
C(CO2Me)2
C(CO2Me)2
C(CO2Me)2
C(CO2Me)2
NTs
Ph/Me/H (1d)
Ph/Me/Me (1e)
Ph/Me/Me (1e)
Me/Ph/H (1f)
Me/Me/H (1g)
Ph/Ph/H (1h)
Ph/Me/H (1i)
Ph/Me/Me (1j)
Ph/Ph/H (1k)
Ph/Me/H (1l)
2
4
2d (80)
2e þ 3e (70)d
2e (47)f
2f (75)
2
4
8
18
7
2g (70)
2h (86)g
2i (94)
solventg time (h) % yieldd
9
entry
catalyst (mol %)
10
11
12
13h
NTs
2
1
2
none
[Rh(CO)2Cl]2
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DMF
CH3CN
EtOH
toluene
24
24
NRh
NTs
7
2j (67)
e
ꢀ
O
2
2k (85)
2l (60)
3b (PPh3)3RhCl/AgSbF6
4b,c [Rh(COD)Cl] 2/AgSbF6
5b [Rh(COD)Cl] 2/AgSbF6
8.0
ꢀ
e
O
3
1.5
0.5
73
a Unless otherwise noted, reactions were performed with 0.2 mmol of 1
and 5 mol % RhCl(IPr)(COD)/AgSbF6 (1:1) in DCE at 75 °C.
b Isolated yields. c The reaction was run at 84 °C. d NMR yields of 59%
for 2e, 24% for 3e, and 9% for 4e. e The reaction was run at 80 °C. f 80%
conversion with NMR yields of 47% for 2e and 27% for 4e. g Confirmed by
X-ray crystallographic analysis. h The reaction was run at 60 °C.
57
NRh
6
[Rh(COD)Cl] 2
12
7c AgSbF6
8c [Rh(η6-C10H8)(COD)]þSbF6
9c [Rh(η6-C6H6)(COD)]þSbF6
10b,c RhCl(IPr)(COD)/AgSbF6
11b,f RhCl(IPr)(COD)/AgSbF6
12b RhCl(IPr)(COD)/AgSbF6
13b RhCl(IMes)(COD)/AgSbF6
1.5
0.5
0.5
ꢀ
e
ꢀ
50
ꢀ
80
36
80 (75)
86 (81)
94 (92)
94 (92)
NRh
results indicate that the present transformation is tolerant of
tethers incorporating geminal diester, sulfonamide, and ether
functionalities. The substituent R1 or R2 can be an aromatic or
alkyl group (entries 1ꢀ8). Compound 1b bearing p-methoxy
group gave [3.1.0] bicyclic compound 2b exclusively in 91%
yield, whereas a reasonable 55% yield of 2c was isolated from 1c
having a p-nitro group on the aromatic R1 substituent, as a result
of the formation of a product isomeric to the epoxide. Epoxide
moieties with a quaternary carbon also afforded the correspond-
ing products in good yields (entries 5 and 11). The structure and
relative stereochemistry of bicyclic 2h were confirmed by X-ray
crystallography analysis.27 It is noteworthy that substrate 1e in
the presence of 5 mol % RhCl(IPr)(COD)/AgSbF6 in DCE for 4
h at 84 °C gave 2e and 3e in 70% yield together with a 9% NMR
yield of the [5 þ 2] cycloadduct 4e (entry 5). When the reaction
was run to 80% conversion, NMR yields of 47% for 2e and 27%
for 4e were obtained, whereas 3e was not observed (entry 6).
Treatment of 4e with 5 mol % RhCl(IPr)(COD)/AgSbF6 in
DCEfor 4hat 84°Cgave2e in 73% NMR yield together with 3e in
16% NMR yield (eq 1), while 2e was obtained as a single
diastereomer uponheatinginthe absenceoftheRh(NHC) catalyst
(eq 2). These results indicate that the Claisen rearrangement of the
[5 þ 2] cycloadducts may take place without the catalyst. To test
whether 3e arose from isomerization of 2e, we subjected 2e to the
reaction conditions in the presence of the Rh(NHC) catalyst.
Surprisingly, NMR yields of 7% for 4e and 26% for 3e were
obtained (eq 3), while treatment of 2e in DCE at 84 °C afforded an
8% NMR yield of 4e (eq 4).28 These results indicate that the
Claisen rearrangement of 4e to 2e is a reversible process under
3.0
2.0
2.0
14
RhCl(IPr)(COD)
24
15b RhCl(IPr)(COD)/AgSbF6
16b RhCl(IPr)(COD)/AgSbF6
17b RhCl(IPr)(COD)/AgSbF6
18b RhCl(IPr)(COD)/AgSbF6
24
24
24
24
ꢀ
e
e
ꢀ
10
80
a Unless otherwise noted, the reaction was performed with 0.2 mmol of1a
and 5 mol % catalyst in 2.5 mL of DCE at 75 °C. b Rh:AgSbF6 = 1:1.
c Reaction was run at room temperature. d Determined by H NMR
1
analysis using CH2Br2 as the internal reference; values in parentheses are
isolated yields. e Complex mixture. f Reaction was run at 60 °C. g DCE =
1,2-dichloroethane, DMF = N,N-dimethylformamide. h NR = no reaction.
presence of [(arene)Rh (COD)]þSbF6 (entries 8 and 9).2e
ꢀ
However, the formation of products isomeric to the epoxides was
also observed. Gratifyingly, the use of 5 mol % RhCl(IPr)-
26
(COD)/AgSbF6 bearing strong σ-donating IPr ligand in
DCE at room temperature provided a 80% NMR yield of 2a
and a 20% NMR yield of 1a. Increasing the temperature to 75 °C
significantly improved the yield to 92% (entries 10ꢀ12). RhCl-
10e
(IMes)(COD)/AgSbF6 was also an efficient catalyst for the
reaction (entry 13). Treatment of 1a with RhCl(IPr)(COD)
alone did not afford the product (entry 14). Different solvents
(entries 15ꢀ18) were also tested but failed to improve the process.
Under the optimal reaction conditions, a series of vinylic
oxiraneꢀalkynes 1 were prepared and examined (Table 2). The
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Journal of the American Chemical Society
COMMUNICATION
Scheme 2
catalyst. Finally, 4 undergoes subsequent Claisen rearrangement to
afford the [3.1.0] bicycle 2.
In summary, an atom-economic route to bicyclo[3.1.0]-
hexanes relying upon a new synthetic application of vinylic
oxiranes in a rhodium-catalyzed intramolecular hetero-[5 þ 2]
cycloaddition/Claisen rearrangement reaction has been de-
scribed. Complete chirality transfer in the present tandem
process was also observed, providing a novel and rapid method
for the synthesis of [3.1.0] bicycles in an enantioselective manner.
Further studies ofthe scope, mechanism, andsynthetic applications
of this new process are underway.
’ ASSOCIATED CONTENT
thermal conditions and that 3e may come from isomerization of 2e
in the presence of the Rh(NHC) catalyst.
S
Supporting Information. Experimental procedures, spec-
b
troscopic data for the substrates and products, and crystallographic
data (CIF) for 2h. This material is available free of charge via the
Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
jlzhang@chem.ecnu.edu.cn
’ ACKNOWLEDGMENT
We are grateful to the NSFC (20972054), the Ministry
of Education of China (20090076110007, NCET), STCSM
(08dj1400100), and the 973 Program (2009CB825300) for
financial support.
’ REFERENCES
In order to gain insight into this transformation, enantiomeri-
cally enriched (þ)-1a (90% ee) was easily prepared and sub-
jected to the current reaction conditions, affording the
corresponding product (þ)-2a in 85% yield with 94% ee
(eq 5). The preservation of the enantiomeric excess in the
product demonstrated complete chirality transfer in the present
tandem hetero-[5 þ 2] cycloaddition/Claisen rearrangement
reaction. Vinylic oxirane 1m lacking an alkyne moiety gave
unstable aldehyde derivative 5m in 75% NMR yield under the
current conditions.15b After reduction, the corresponding alco-
hol 6m was isolated in 49% yield (eq 6). These results suggest
that the cycloaddition proceeds through a mechanism different
from that for the vinylcyclopropane analogues.2f
(1) (a) Ojima, I.; Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem.
Rev. 1996, 96, 635. (b) Lautens, M.; Klute, W.; Tam, W. Chem. Rev.
1996, 96, 49. (c) Yet, L. Chem. Rev. 2000, 100, 2963. (d) Aubert, C.;
Buisine, O.; Malacria, M. Chem. Rev. 2002, 102, 813. (e) Nakamura, I.;
Yamamoto, Y. Chem. Rev. 2004, 104, 2127.
(2) (a) Wender, P. A.; Takahashi, H.; Witulski, B. J. Am. Chem. Soc.
1995, 117, 4720. (b) Wender, P. A.; Husfeld, C. O.; Langkopf, E.; Love,
J. A. J. Am. Chem. Soc. 1998, 120, 1940. (c) Wender, P. A.; Glorius, F.;
Husfeld, C. O.; Langkopf, E.; Love, J. A. J. Am. Chem. Soc. 1999,
121, 5348. (d) Wender, P. A.; Dyckman, A. J. Org. Lett. 1999, 1, 2089.
(e) Wender, P. A.; Williams, T. J. Angew. Chem., Int. Ed. 2002, 41, 4550.
(f) Yu, Z.-X.; Wender, P. A.; Houk, K. N. J. Am. Chem. Soc. 2004,
126, 9154. (g) Wender, P. A.; Stemmler, R. T.; Sirois, L. E. J. Am. Chem.
Soc. 2010, 132, 2532. For Rh-catalyzed intermolecular hetero-[5 þ 2]
cycloadditions of cyclopropylimines and alkynes, see: (h) Wender, P. A.;
Pedersen, T. M.; Scanio, M. J. C. J. Am. Chem. Soc. 2002, 124, 15154.
(i) Montero-Campillo, M. M.; Cabaleiro-Lago, E. M.; Rodríguez-Otero,
J. J. Phys. Chem. A 2008, 112, 9068. For a review, see: (j) Wender, P. A.;
Gamber, G. G.; Williams, T. J. In Modern Rhodium-Catalyzed Organic
Reactions; Evans, P. A., Ed.; Wiley-VCH: Weinheim, Germany, 2005;
pp 263 ff and references cited therein.
(3) (a) Trost, B. M.; Toste, F. D.; Shen, H. J. Am. Chem. Soc. 2000,
122, 2379. (b) Trost, B. M.; Shen, H. C. Angew. Chem., Int. Ed. 2001,
40, 2313. (c) Trost, B. M.; Shen, H. C. Org. Lett. 2000, 2, 2523. (d) Trost,
B. M.; Shen, H. C.; Schulz, T.; Koradin, C.; Schirok, H. Org. Lett. 2003,
5, 4149. (e) Trost, B. M.; Shen, H. C.; Horne, D. B.; Toste, F. D.;
Steinmetz, B. G.; Koradin, C. Chem.—Eur. J. 2005, 11, 2577. (f) Trost,
B. M.; Waser, J.; Meyer, A. J. Am. Chem. Soc. 2007, 129, 14556.
(4) (a) Jiao, L.; Yuan, C.; Yu, Z.-X. J. Am. Chem. Soc. 2008, 130, 4421.
(b) Fan, X.; Zhuo, L.-G.; Tu, Y. Q.; Yu, Z.-X. Tetrahedron 2009,
65, 4709. (c) Jiao, L.; Lin, M.; Yu, Z.-X. Chem. Commun. 2010,
46, 1059. (d) Jiao, L.; Ye, S.; Yu, Z.-X. J. Am. Chem. Soc. 2008,
130, 7178. (e) Li, Q.; Jiang, G.-J.; Jiao, L.; Yu, Z.-X. Org. Lett. 2010,
On the basis of the above observations, one proposed mechan-
ism is depicted in Scheme 2.The coordinated intermediate A is
formed by the coordination of enyne 1 with a cationic Rh(I)
species generated in situ. Oxidative cyclometalation of the enyne
affords rhodacyclopentane B. Subsequent β-O elimination from B
yields the CꢀRhꢀO species C.29 Reductive elimination from this
species produces 2,5-dihydrooxepin 4 and regenerates the rhodium
7306
dx.doi.org/10.1021/ja2014604 |J. Am. Chem. Soc. 2011, 133, 7304–7307

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12, 1332. (f) Jiao, L.; Lin, M.; Zhuo, L.-G.; Yu, Z.-X. Org. Lett. 2010,
12, 2528. (g) Jiao, L.; Lin, M.; Yu, Z.-X. J. Am. Chem. Soc. 2011,
133, 447. (h) Lin, M.; Li, F.; Jiao, L.; Yu, Z.-X. J. Am. Chem. Soc. 2011,
133, 1690.
(5) For reviews of [4 þ 3] cycloadditions, see: (a) Harmata, M. Chem.
Commun. 2010, 46, 8904. (b) Harmata, M. Chem. Commun. 2010,
46, 8886. (c) Battiste, M. A.; Pelphrey, P. M.; Wright, D. L. Chem.—Eur.
J. 2006, 12, 3438. (d) Hartung, I. V.; Hoffmann, H. M. R. Angew. Chem., Int.
Ed. 2004, 43, 1934. (e) Cha, J. K.; Oh, J. Curr. Org. Chem. 1998, 2, 217.
(6) (a) Lautens, M.; Ren, Y.; Delanghe, P. H. M. J. Am. Chem. Soc. 1994,
116, 8821. (b) Lautens, M.; Ren, Y. J. Am. Chem. Soc. 1996, 118, 9597.
(7) Corlay, H.; Lewis, R. T.; Motherwell, W. B.; Shipman, M.
Tetrahedron Lett. 1995, 51, 3303.
102, 2095. (g) Hirao, T.; Yamada, N.; Ohshiro, Y.; Agawa, T. Chem.
Lett. 1982, 1997. (h) Vankar, Y. D.; Chaudhuri, N. C.; Singh, S. P. Synth.
Commun. 1986, 16, 1621. (i) Visentin, G.; Piccolo, O.; Consiglio, G.
J. Mol. Catal. 1990, 61, L1. (j) Kulasegaram, S.; Kulawiec, R. J. J. Org.
Chem. 1997, 62, 6547. For a review, see: (k) Rickborn, B. In
Comprehensive Organic Synthesis; Trost, B. M., Ed.; Pergamon: Oxford,
U.K., 1991; Vol. 3; Chapter 3.3, pp 733 ff. (l) Parker, R. E.; Isaacs, N. S.
Chem. Rev. 1959, 59, 737. (m) Crawford, R. J.; Lutener, S. B.; Cockcroft,
R. D. Can. J. Chem. 1976, 54, 3364. (n) Batory, L. A.; McInnis, C. E.;
Njardarson, J. T. J. Am. Chem. Soc. 2006, 128, 16054. (o) Brichacek, M.;
Batory, L. A.; Njardarson, J. T. Angew. Chem., Int. Ed. 2010, 49, 1648.
(16) (a) Trost, B. M.; Angle, S. R. J. Am. Chem. Soc. 1985, 107, 6123.
(b) Shim, J.-G.; Yamamoto, Y. J. Org. Chem. 1998, 63, 3067.
(17) (a) Zhang, Y.; Chen, Z.; Xiao, Y.; Zhang, J. Chem.—Eur. J. 2009,
15, 5208. (b) Fan, L.; Zhao, W.; Jiang, W.; Zhang, J. Chem.—Eur. J. 2008,
14, 9139. (c) Zhao, W.; Zhang, J. Chem. Commun. 2010, 46, 4384.
(d) Zhao, W.; Zhang, J. Chem. Commun. 2010, 46, 7816. (e) Zhao, W.;
Zhang, J. Org. Lett. 2011, 13, 688. (f) Wang, T.; Zhang, J. Chem.—Eur. J.
2011, 17, 86. (g) Chen, Z.; Wei, L.; Zhang, J. Org. Lett. 2011, 13, 1170.
(18) (a) Rhoads, S. J.; Cockroft, R. D. J. Am. Chem. Soc. 1969,
91, 2815. (b) Rey, M.; Dreiding, A. S. Helv. Chim. Acta 1965, 48, 1985.
(c) Ziegler, F. E. Chem. Rev. 1988, 88, 1423. (d) Castro, A. M. M. Chem.
Rev. 2004, 104, 2939.
(8) Yamago, S.; Nakamura, E. J. Chem. Soc., Chem. Commun. 1988,
1112.
(9) (a) Bhargava, G.; Trillo, B.; Araya, M.; Lꢀopez, F.; Castedo, L.;
Mascare~nas, J. L. Chem. Commun. 2010, 46, 270. (b) Gulias, M.; Duran,
J.; Lꢀopez, F.; Castedo, L.; Mascare~nas, J. L. J. Am. Chem. Soc. 2007,
129, 11026. (c) Saya, L.; Bhargava, G.; Navarro, M. A.; Gulias, M.;
Lꢀopez, F.; Fernandez, I.; Castedo, L.; Mascare~nas, J. L. Angew. Chem., Int.
Ed. 2010, 49, 9886.
(10) (a) Evans, P. A.; Sawyer, J. R.; Lai, K. W.; Huffman, J. C. Chem.
Commun. 2005, 3971. (b) Evans, P. A.; Lai, K. W.; Sawyer, J. R. J. Am.
Chem. Soc. 2005, 127, 12466. (c) Evans, P. A.; Robinson, J. E.; Baum,
E. W.; Fazal, A. N. J. Am. Chem. Soc. 2002, 124, 8782. Evans, P. A.;
Robinson, J. E.; Baum, E. W.; Fazal, A. N. J. Am. Chem. Soc. 2003,
125, 14648. (d) Evans, P. A.; Baum, E. W. J. Am. Chem. Soc. 2004,
126, 11150. (e) Evans, P. A.; Baum, E. W.; Fazal, A. N.; Pink, M. Chem.
Commun. 2005, 63. (f) Baik, M.-H.; Baum, E. W.; Burland, M. C.; Evans,
P. A. J. Am. Chem. Soc. 2005, 127, 1602.
(19) (a) Liu,H.-W.;Walsh,C.T.InThe Chemistry of the Cyclopropyl Group;
Rappoport, Z., Ed.; Wiley: New York, 1987; pp 959 ff. (b) Bueno, A. B.; J. Med.
Chem. 2005, 48, 5305. (c) McBriar, M. D.; J. Med. Chem. 2006, 49, 2294.
(20) (a) Doyle, M. P.; Forbes, D. C. Chem. Rev. 1998, 98, 911.
(b) Davies, H. W. L.; Antoulinakis, E. G. Org. React. 2001, 57, 1.
(c) Maas, G. Chem. Soc. Rev. 2004, 33, 183 and references cited therein.
(21) For example, see: Bremeyer, N.; Smith, S. C.; Ley, S. V.; Gaunt,
M. J. Angew. Chem., Int. Ed. 2004, 43, 2681.
(11) (a) Sagae, H.; Noguchi, K.; Hirano, M.; Tanaka, K. Chem.
Commun. 2008, 3804. (b) Nishida, G.; Noguchi, K.; Hirano, M.; Tanaka,
K. Angew. Chem., Int. Ed. 2008, 47, 3410. (c) Tanaka, K.; Fukawa, N.;
Suda, T.; Noguchi, K. Angew. Chem., Int. Ed. 2009, 48, 5470. (d) Tanaka,
K. Chem.—Asian J. 2009, 4, 508 and references cited therein.
(12) For selected examples, see: (a) Kablaoui, N. M.; Hicks, F. A.;
Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 5818. (b) Kablaoui, N. M.;
Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1997, 119, 4424.
(c) Chatani, N.; Morimoto, T.; Fukumoto, Y.; Murai, S. J. Am. Chem.
Soc. 1998, 120, 5335. (d) Trost, B. M.; Brown, R. E.; Toste, F. D. J. Am.
Chem. Soc. 2000, 122, 5877. (e) Saito, A.; Hironaga, M.; Oda, S.;
Hanzawa, Y. Tetrahedron Lett. 2007, 48, 6852. (f) Shintani, R.; Fu, G. C.
J. Am. Chem. Soc. 2003, 125, 10778. (g) Liu, F.; Yu, Y.; Zhang, J. Angew.
Chem., Int. Ed. 2009, 48, 5505. (h) Liu, F.; Qian, D.; Li, L.; Zhao, X.;
Zhang, J. Angew. Chem., Int. Ed. 2010, 49, 6669. (i) R€uck-Braun, K.;
Freysoldt, T. H. E.; Wierschem, F. Chem. Soc. Rev. 2005, 34, 507.
(j) Cardona, F.; Goti, A. Angew. Chem., Int. Ed. 2005, 44, 7832. (k) Yu,
R. T.; Rovis, T. J. Am. Chem. Soc. 2006, 128, 2782–2783. (l) Perreault, S.;
Rovis, T. Chem. Soc. Rev. 2009, 38, 3149 and references cited therein.
(13) (a) Aldous, D. J.; Batsanov, A. S.; Yufit, D. S.; Dalencon, A. J.;
Dutton, W. M.; Steel, P. G. Org. Biomol. Chem. 2006, 4, 2912. (b) Ley,
S. V.; Burckhardt, S.; Cox, L. R.; Meek, G. J. Chem. Soc., Perkin Trans. 1
1997, 3327. (c) Marschall, H.; Penninger, J.; Weyerstahl, P. Liebigs
Ann. Chem. 1982, 1, 49. (d) Marigo, M.; Franzꢀen, J.; Poulsen, T. B.;
Zhuang, W.; Jørgensen, K. A. J. Am. Chem. Soc. 2005, 127, 6964.
(e) Matsuo, J.-I.; Iida, D.; Yamanaka, H.; Mukaiyama, T. Tetrahedron
2003, 59, 6739.
(22) (a) Simmons, H. E.; Smith, R. D. J. Am. Chem. Soc. 1958,
80, 5323. (b) Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993,
93, 1307. (c) Bull, J. A.; Charette, A. B. J. Am. Chem. Soc. 2010, 132, 1895.
(23) (a) Hodgson, D. M.; Chung, Y. K.; Paris, J.-M. J. Am. Chem. Soc.
2004, 126, 8664. (b) Hodgson, D. M.; Chung, Y. K.; Nuzzo, I.; Freixas,
G.; Kulikiewicz, K. K.; Cleator, E.; Paris, J.-M. J. Am. Chem. Soc. 2007,
129, 4456.
(24) For other examples, see: (a) Ogawa, A.; Takami, N.; Sekiguchi,
M.; Ryu, I.; Kambe, N.; Sonoda, N. J. Am. Chem. Soc. 1992, 114, 8729.
(b) Madelaine, C.; Ouhamou, N.; Chiaroni, A.; Vedrenne, E.; Grimaud,
L.; Six, Y. Tetrahedron 2008, 64, 8878. (c) Harvey, D. F.; Lund, K. P.;
Neil, D. A. J. Am. Chem. Soc. 1992, 114, 8424. (d) Yang, D.; Gao, Q.; Lee,
C.-S.; Cheung, K.-K. Org. Lett. 2002, 4, 3271. (e) Taber, D. F.; Guo, P.;
Guo, N. J. Am. Chem. Soc. 2010, 132, 11179.
(25) Using Pt: (a) Harrak, Y.; Blaszykowski, C.; Bernard, M.; Cariou,
K.; Mainetti, E.; Mouriꢁes, V.; Dhimane, A.-L.; Fensterbank, L.; Malacria,
M. J. Am. Chem. Soc. 2004, 126, 8656. (b) Mamane, V.; Gress, T.; Krause,
H.; F€urstner, A. J. Am. Chem. Soc. 2004, 126, 8654. Using Au:
(c) Luzung, M. R.; Markham, J. P.; Toste, F. D. J. Am. Chem. Soc. 2004,
126, 10858. (d) Buzas, A.; Gagosz, F. J. Am. Chem. Soc. 2006, 128, 12614.
Using Pd: (e) Welbes, L. L.; Lyons, T. W.; Cychosz, K. A.; Sanford, M. S.
J. Am. Chem. Soc. 2007, 129, 5836. (f) Tong, X. F.; Beller, M.; Tse, M. K.
J. Am. Chem. Soc. 2007, 129, 4906. Using Rh: (g) Miura, T.; Sasaki, T.;
Harumashi, T.; Murakami, M. J. Am. Chem. Soc. 2006, 128, 2516. For a
review, see: (h) Bruneau, C. Angew. Chem., Int. Ed. 2005, 44, 2328.
(26) Lee, S. I.; Park, S. Y.; Park, J. H.; Jung, I. G.; Choi, S. Y.; Chung,
Y. K.; Lee, B. Y. J. Org. Chem. 2006, 71, 91.
(14) (a) Miyashita, M.; Mizutani, T.; Tadano, G.; Iwata, Y.; Miyazawa,
M.; Tanino, K. Angew. Chem., Int. Ed. 2005, 44, 5094. (b) Trost, B. M.; Bunt,
R. C.; Lemoine, R. C.; Calkins, T. L. J. Am. Chem. Soc. 2000, 122, 5968.
(c) Fagnou, K.; Lautens, M. Org. Lett. 2000, 2, 2319 and references cited
therein.
(27) CCDC 813196 contains the supplementary crystallographic
data for 2h in this paper. These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
datarequest/cif.
(28) However, no reaction occurred upon treatment of 2a with
5 mol% RhCl(IPr)(COD)/AgSbF6 in DCE for 4 h at 75 °C. This is the
reason that we did not isolate the corresponding 2,5-dihydrooxepin.
(29) Odedra, A.; Wu, C.-J.; Madhushaw, R. J.; Wang, S.-L.; Liu, R.-S.
J. Am. Chem. Soc. 2003, 125, 9610.
(15) (a) Adames, G.; Bibby, C.; Grigg, R. J. Chem. Soc., Chem.
Commun. 1972, 491. (b) Milstein, D.; Buchman, O.; Blum, J. J. Org.
Chem. 1977, 42, 2299. (c) Milstein, D. J. Am. Chem. Soc. 1982, 104, 5227.
(d) Chen, J.; Che, C.-M. Angew. Chem., Int. Ed. 2004, 43, 4950.
(e) Suzuki, M.; Oda, Y.; Noyori, R. J. Am. Chem. Soc. 1979, 101, 1623.
(f) Suzuki, M.; Watanabe, A.; Noyori, R. J. Am. Chem. Soc. 1980,
7307
dx.doi.org/10.1021/ja2014604 |J. Am. Chem. Soc. 2011, 133, 7304–7307