Auto-Tandem Cooperative Catalysis Using Phosphine/Palladium: Reaction of Morita–Baylis–Hillman Carbonates and Allylic Alcohols

Article abstract of DOI:10.1002/anie.201814403

Auto-tandem catalysis (ATC), in which a single catalyst promotes two or more mechanistically different reactions in a cascade pattern, provides a powerful strategy to prepare complex products from simple starting materials. Reported here is an unprecedented auto-tandem cooperative catalysis (ATCC) for Morita–Baylis–Hillman carbonates from isatins and allylic carbonates using a simple Pd(PPh₃)₄ precursor. Dissociated phosphine generates phosphorus ylides and the Pd leads to π-allylpalladium complexes, and they undergo a γ-regioselective allylic–allylic alkylation reaction. Importantly, a cascade intramolecular Heck-type coupling proceeds to finally furnish spirooxindoles incorporating a 4-methylene-2-cyclopentene motif. Experimental results indicate that both Pd and phosphine play crucial roles in the catalytic Heck reaction. In addition, the asymmetric versions with either a chiral phosphine or chiral auxiliary are explored, and moderate results are obtained.

Full text of DOI:10.1002/anie.201814403

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Auto-Tandem Cooperative Catalysis of Phosphine/Palladium for
Carbonates of Morita−Baylis−Hillman and Allylic Alcohols
Authors: Ying-Chun Chen, Peng Chen, Zhi-Chao Chen, Yue Li, Qin
Ouyang, and Wei Du
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201814403
Angew. Chem. 10.1002/ange.201814403
Link to VoR: http://dx.doi.org/10.1002/anie.201814403
http://dx.doi.org/10.1002/ange.201814403

10.1002/anie.201814403
Angewandte Chemie International Edition
COMMUNICATION
Auto-Tandem Cooperative Catalysis Using Phosphine/Palladium:
Reaction of MoritaBaylisHillman Carbonates and Allylic
Alcohols
Peng Chen, Zhi-Chao Chen, Yue Li, Qin Ouyang, Wei Du,* and Ying-Chun Chen*
Abstract: Auto-tandem catalysis (ATC), in which a single catalyst
promotes two or more mechanistically different reactions in a cascade
pattern, provides a powerful strategy to prepare complex products
from simple starting materials. Here, we report an unprecedented
auto-tandem cooperative catalysis (ATCC) for MoritaBaylisHillman
carbonates from isatins and allylic carbonates with simple Pd(PPh3)4
precursor. Dissociated phosphine-mediated phosphorus-ylides and -
allylpalladium complexes are independently generated, which
decades, especially under the activation of Lewis base (LB)
catalysts, by generating either electrophilic salts I or allylic ylides
II (Scheme 1a).[6] Since MBH products possess an allylic alcohol
motif, their acylates or carbonates have a long history to be
utilized in allylic alkylation reactions by forming -allylpalladium
complexes III (Scheme 1b).[7] As a result, it would be highly
challenging by chemoselectively combining Lewis base-activated
intermediates of MBH derivatives with active -allylpalladium
species generated from other allyl derivatives. In fact, there is
even no successful report dealing with cooperative catalysis for
MBH derivatives under organo and metal catalysis to date.[8] In
our continuing interest in developing new transformations of MBH
derivatives,[9] here we would like to disclose that highly
chemoselective activations of MBH carbonates from isatins and
allylic carbonates could be accomplished by tertiary phosphine/
Pd(0) complex, respectively, for the first time, as illustrated in
Scheme 1c. Thus, -regioselective allylic-allylic alkylation
between IV and V occurred accordingly. Moreover, an unusual
tandem catalytic intramolecular Heck-type coupling reaction was
followed to furnish a [3+2] annulation process (Scheme 1c).
undergo
a
-regioselective allylic-allylic alkylation reaction.
Importantly, a cascade intramolecular Heck-type coupling is followed
between the resulting alkene-phosphonium groups, finally furnishing
spirooxindoles incorporating a 4-methylene-2-cyclopentene motif.
Experiment results indicate that both Pd and phosphine play crucial
roles in the catalytic Heck reaction. In addition, the asymmetric
versions with chiral phosphine or chiral auxiliary are explored, and
moderate results are obtained.
The catalytic tandem reaction, in which two or more
transformations occur consecutively thus avoiding the tedious
isolation and purification of intermediates, provides a powerful
approach to produce complicated substances from simple starting
materials.[1] As mechanistically distinct processes are usually
encountered, dual or even multiple catalytic systems are
commonly employed to promote the designed reactions.[2] It
would be highly facilitating that a single catalyst can efficiently
mediate the tandem reactions involving the conversions of
different functionalities in the substrates, previously defined as
auto-tandem catalysis (ATC) by Fogg and dos Santos.[3]
Significant progress has been made in this field by utilizing metal
or small organic molecule catalysts.[4] On the other hand, organic
chemists also have devoted great effort to develop effective
reactions by merging the cooperative or relay activation modes of
different metal and organic catalysts.[5] Nevertheless, there is still
no example involving auto-tandem cooperative catalysis (ATCC)
of both metal and organocatalyst in a cascade process.
The MoritaBaylisHillman (MBH) products, condensed from
activated alkenes and carbonyl compounds, have found
extensive applications in latent transformations over the past
Scheme 1. Lewis base and Pd activation strategies for MBH derivatives.
[a]
P. Chen, Z.-C. Chen, Y. Li, Dr. W. Du, Prof. Dr. Y.-C. Chen
Key Laboratory of Drug-Targeting and Drug Delivery System of the
Ministry of Education and Sichuan Research Center for Drug
Precision Industrial Technology
The initial reaction of MBH carbonate 1a and allyl benzoate
2a proceeded smoothly in THF in the presence of catalytic
amounts of Pd(PPh3)4, but gave an inseparable mixture of
spirooxindole 3a (R = Me) and 1,3-difunctionalization product[10]
4a (R = Me) (Table 1, entry 1). It seems that MBH carbonate 1a
and allyl benzoate 2a were independently activated by
dissociated PPh3 and Pd(0) complex, respectively (Scheme 1c).
After the desired allylic alkylation reaction, an annulation or
alternative benzoate addition-elimination process was followed.
Pleasingly, replacing 1a with a more bulky substrate 1b
West China School of Pharmacy, Sichuan University
Chengdu, 610041 (China)
Fax: (+) 86 28 85502609
E-mail: duweiyb@scu.edu.cn; ycchen@scu.edu.cn
Prof. Dr. Q. Ouyang, Prof. Dr. Y.-C. Chen
College of Pharmacy, Third Military Medical University
Chongqing 400038 (China)
[b]
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
This article is protected by copyright. All rights reserved.

10.1002/anie.201814403
Angewandte Chemie International Edition
COMMUNICATION
exclusively delivered the spiro product 3b (R = tBu) in a high yield
(Table 1, entry 2). Adding catalytic amounts of DABCO or DMAP
apparently reduced the yield (Table 1, entries 3 and 4). The
combination of PPh3 and Pd2(dba)3 also efficiently promoted the
reaction (Table 1, entry 5); in contrast, 3b was obtained by using
DABCO or DMAP with Pd2(dba)3 (Table 1, entries 6 and 7). These
results suggested that phosphine was crucial for the annulation
reaction. Moreover, sole Pd2(dba)3 or PPh3 could not promote the
reaction, identifying the importance of the cooperative catalysis
(Table 1, entry 8 and 9). In addition, [Pd(allyl)Cl]2 was not a
successful palladium source (Table 1, entry 10). Subsequently, it
was found that even a higher yield was attained by assembling
MBH carbonate 1b and allyl carbonate 2b catalyzed by Pd(PPh3)4
(Table 1, entry 11). Nevertheless, employing less amounts of 2b
afforded a reduced yield (Table 1, entry 12). Notably, the tandem
annulation still proceeded effectively by significantly diminishing
the catalyst loadings (Table 1, entries 13 and 14).
carbonates 1 with electron-withdrawing groups exhibited lower
reactivity, whereas outstanding yields were gained at higher
temperature and catalyst loadings (Table 2, entries 57).
Excellent yields were also produced for MBH carbonates 1
derived from N-methyl isatins (Table 2, entries 810). A high yield
was attained for a MBH carbonate from ethyl acrylate (Table 2,
entry 11), but the yield was only moderate for a MBH carbonate
from vinyl methyl ketone (Table 2, entry 12). In addition, a MBH
carbonate from 7-azaisatin was tested, also giving a high yield
(Table 2, entry 13).[11]
Table 2. Substrate scope of the tandem reactions of MBH carbonates 1 and
allyl carbonate 2b.[a]
Table 1. Screening conditions of the reactions of MBH carbonates 1 and allyl
derivatives 2.[a]
Entry
1
R
H
R1, R2
t (h)
Yield (%)[b]
Bn, tBuO
12
3b, 90
2
5-MeO
7-Me
5,7-Me2
5-F
Bn, tBuO
Bn, tBuO
Bn, tBuO
Bn, tBuO
Bn, tBuO
Bn, tBuO
Me, tBuO
Me, tBuO
Me, tBuO
Bn, EtO
36
36
36
36
36
36
36
36
36
36
12
24
3c, 97
3d, 93
3e, 97
3f, 96
3g, 93
3h, 93
3i, 97
3j, 92
3k, 91
3l, 91
3m, 70
3n, 85
3
4
5[c,d]
6[c,d]
7[c,d]
8
Entry
1[c]
2
LB
/
[Pd]
Yield (%)[b]
2a
Pd(PPh3)4
3a+4a, 84
6-Br
7-Br
H
2
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
2b
2b
2b
/
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
Pd2(dba)3
/
3b, 89
3b, 75
3b, 52
3b, 80
/
3
DABCO
4
DMAP
9
5-Me
5-MeO
H
5
PPh3
10
11
12[c]
13[c,e]
6
DABCO
7
DMAP
/
H
Me, Me
8
/
/
H
Bn, tBuO
9
PPh3
/
[a] Unless noted otherwise, reactions were performed with MBH carbonate 1 (X
= CH) (0.1 mmol), 2b (0.2 mmol), Pd(PPh3)4 (2.5 mol%) in THF (1.0 mL) at rt.
[b] Isolated yield. [c] With 5 mol% Pd(PPh3)4. [d] At 35 C. [e] With MBH
carbonate 1 from 7-azaisatin (X = N).
10
11
12[d]
13[e]
14[f]
PPh3
[Pd(allyl)Cl]2
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
3b, <5
3b, 93
3b, 78
3b, 90
3b, 87
/
/
/
/
Subsequently, we investigated the substrate scope of allylic
carbonate partners 2. As illustrated in Table 3, an array of diverse
aryl-substituted allylic carbonates 2 showed good reactivity in
assembly with MBH carbonate 1b at ambient temperature under
the catalysis of Pd(PPh3)4 (5 mol%), and the corresponding
spirooxindoles 3o3x were generally obtained in good yields with
exclusive stereoselectivity.[12] Moderate to high yields were also
produced with 2-naphthyl or heteroaryl-substituted allylic
carbonates (products 3y3bb). Nevertheless, alkynyl- or vinyl-
substituted allylic carbonates exhibited lower reactivity even at
higher temperature, and only fair yields for products 3bc3be
were furnished, with excellent stereoselectivity too. The alkyl-
substituted ones could be utilized though with low reactivity, and
a mixture of deconjugated and conjugated diene products 3bf and
3bg were generated in fair yields. The carbonate of E-4-
phenylbut-3-en-2-ol could be used, whereas the product 3bh was
provided as a diastereomeric mixture in a low yield.
[a] Unless noted otherwise, reactions were performed with MBH carbonate 1b
(0.1 mmol), 2 (0.2 mmol), [Pd] source (5 mol%), LB (20 mol%) in THF (1.0 mL)
at rt for 12 h. [b] Isolated yield. [c] With 1a, 3a/4a = 5:1. [d] With 0.15 mmol 2b.
[e] With 2.5 mol% Pd(PPh3)4. [f] With 1.0 mol% Pd(PPh3)4. THF = tetrahydro-
furan; dba = dibenzylideneacetone; DABCO = 1,4-diazabicyclo[2.2.2]octane;
DMAP = 4-dimethylaminopyridine; Boc = tert-butyloxycarbonyl; Bz = benzoyl.
With the optimal catalytic conditions in hand, the substrate
scope and limitations of this new tandem reaction were explored.
The results are summarized in Table 2. A few MBH carbonates 1
derived from electron-donating substituted N-benzyl isatins and t-
butyl acrylate reacted effectively with allyl carbonate 2b under the
catalysis of Pd(PPh3)4 (2.5 mol%), and excellent yields were
obtained after a longer time (Table 2, entries 24). The MBH
This article is protected by copyright. All rights reserved.

10.1002/anie.201814403
Angewandte Chemie International Edition
COMMUNICATION
2). In addition, the MBH carbonate 1c derived from R-menthyl
acrylate exhibited good reactivity with carbonate 2b or 2c in the
presence of Pd(PPh3)4, and modest diastereoselectivity was
observed (3bi and 3bj). Moreover, better diastereocontrol was
obtained by using Pd2(dba)3 and chiral phosphine P2 or P3.
Table 3. Substrate scope and limitations of the tandem reactions of MBH
carbonates 1 and allylic carbonates 2.[a,b]
Scheme 3. Synthetic transformation of product 3l.
As outlined in Scheme 3, the regioselective 1,3-dipolar
cycloaddition of 3l and 5 was efficiently conducted, affording spiro
and fused product 6 in excellent diastereoselectivity.
[a] Unless noted otherwise, reactions were performed with MBH carbonate 1
(0.1 mmol), 2 (0.25 mmol), Pd(PPh3)4 (5 mol%) in THF (1.0 mL) at rt. [b] Isolated
yield.
Scheme 4. Mechanism elucidation of the proposed reaction process.
In order to gain some insight into the cooperative catalysis,
more experiments were conducted. As outlined in Scheme 4a, the
combination of Pd2(dba)3 and R-BINAP P4 could not promote the
reaction of 1b and 2b (entry 1), and the similar results were
observed by further adding PPh3 (entry 2), indicating a chelating
bisphosphine ligand would inhibit the process. Such a conclusion
was further confirmed by replacing P4 with monooxide P5, which
gave a high yield of 3b (entry 3). Notably, the allylic alkylation of
MBH carbonate 1b and benzoate 2a was facilitated under the
cooperative catalysis of Pd2(dba)3, bisphosphine P4 and DABCO,
and the product 4b was obtained in a moderate yield (entry 4).[10]
Even higher yield and enantioselectivity were attained with chiral
Scheme 2. Asymmetric tandem reactions.
A
number of commonly used chiral phosphines in
combination with Pd2(dba)3 failed to promote the reaction of 1b
and 2b.[13] Fortunately, the newly designed monophosphines
derived from L-proline showed high activity, and moderate
enantioselectivity with a high yield was obtained with P1 (Scheme
This article is protected by copyright. All rights reserved.

10.1002/anie.201814403
Angewandte Chemie International Edition
COMMUNICATION
tertiary amine L1 (entry 5).[13] These results further verify that a
phosphine-type Lewis base is essential for the tandem annulation
reaction, and support that spiro 3b would not result from an ene-
type addition-phosphine elimination sequence.
[3]
[4]
For selected reviews, see: a) D. E. Fogg, E. N. dos Santos, Coord. Chem.
Rev. 2004, 248, 2365; b) N. Shindoh, Y. Takemoto, K. Takasu, Chem.
Eur. J. 2009, 15, 12168: c) J. E. Camp, Eur. J. Org. Chem. 2017, 425.
For related reviews, see: a) H. Ohno, Israel J. Chem. 2013, 53, 869; b)
H. Pellissier, Adv. Synth. Catal. 2016, 358, 2194; c) C. M. R. Volla, I.
Atodiresei, M. Rueping, Chem. Rev. 2014, 114, 2390; d) P. Chauhan, S.
Mahajan, D. Enders, Acc. Chem. Res. 2017, 50, 2809; e) T. Chanda, J.
C.-G. Zhao, Adv. Synth. Catal. 2018, 360, 2; for selected examples, see:
f) N. Kanbayashi, K. Takenaka, T.-a. Okamura, K. Onitsuka, Angew.
Chem. Int. Ed. 2013, 52, 4897; Angew. Chem. 2013, 125, 4997; g) S.
Das, D. Hong, Z. Chen, Z. She, W. H. Hersh, G. Subramaniam, Y. Chen,
Org. Lett. 2015, 17, 5578; h) A. R. O. Venning, M. R. Kwiatkowski, J. E.
Roque Peña, B. C. Lainhart, A. A. Guruparan, E. J. Alexanian, J. Am.
Chem. Soc. 2017, 139, 11595; i) M. Bakos, Á. Gyömöre, A. Domján, T.
Soós, Angew. Chem. Int. Ed. 2017, 56, 5217; Angew. Chem. 2017, 129,
5301; j) A. Kondoh, M. Terada, Org. Lett. 2018, 20, 5309.
Consequently, a plausible mechemism was proposed for the
reaction of 1b and 2b (Scheme 4b). The initial chemoselective
reaction of allyl carbonate 2b and Pd(PPh3)4 would produce the
expected -allylpalladium complex A. The dissociated PPh3
would attack MBH carbonate 1b to favorably generate E-
configured allylic P-ylide species B. Thus, the -regioselective
allylic alkylation would occur via cooperative catalysis. Next, the
key oxidative addition between olefin-complexed Pd(0) and
phosphonium groups in species C (Pd-decompelxed cation was
detected by HRMS analysis) would deliver intermediate D.[14]
Therefore, the classical Heck coupling would happen to afford
intermediate E, and produce the observed spirooxindole 3b after
a reductive -elimination process. Thus, PPh3 would act as an
unusual catalyst in the Pd-catalyzed Heck-type coupling by
forming active phosphonium species with MBH carbonate 1b,
rendering the current reaction proceed via unprecedented auto-
tandem cooperative catalysis.
In conclusion, we first demonstrated that highly chemo-
selective activations for MBH carbonates from isatins and allylic
carbonates could be realized by Lewis basic tertiary phosphine
and Pd(0) complex, respectively, by employing simple Pd(PPh3)4
as catalyst precursor. After the cooperative catalytic allylic
alkylation reaction, a auto-tandem intramolecular Pd-catalyzed
Heck coupling reaction occurred between the resulting alkene
and phosphonium functionalities, finally constructing a spectrum
of spirooxindoles incorporating a 4-methylene-2-cyclopentene
motif. This work represents a quite intriguing study, in which a
cascade process containing mechanistically different reactions is
realized via unprecedented and challenging auto-tandem
cooperative catalysis (ATCC) of organic substance and metal
complex. We believe that this study would arouse broad interest
in the field of catalysis. More results will be reported in due course.
[5]
[6]
[7]
For selected reviews, see: a) C. Zhong, X. Shi, Eur. J. Org. Chem. 2010,
2999; b) Z. Du, Z. Shao, Chem. Soc. Rev. 2013, 42, 1337; c) D.-F. Chen,
Z.-Y. Han, X.-L. Zhou, L.-Z. Gong, Acc. Chem. Res. 2014, 47, 2365; d)
S. Afewerki, A. Córdova, Chem. Rev. 2016, 116, 13512.
For reviews, see: a) R. Rios, Catal. Sci. Technol. 2012, 2, 267; b) T.-Y.
Liu, M. Xie, Y.-C. Chen, Chem. Soc. Rev. 2012, 41, 4101; c) Y. Wei, M.
Shi, Chem. Rev. 2013, 113, 6659; d) P. Xie, Y. Huang, Org. Biomol.
Chem. 2015, 13, 8578; e) H. Pellissier, Tetrahedron 2017, 73, 2831.
For selected reviews, see: a) B. M. Trost, Chem. Pharm. Bull. 2002, 50,
1; b) B. M. Trost, M. R. Machacek, A. Aponick, Acc. Chem. Res. 2006,
39, 747; for selected examples, see: c) B. M. Trost, F. D. Toste, J. Am.
Chem. Soc. 1998, 120, 815; d) B. M. Trost, H. C. Tsui, F. D. Toste, J.
Am. Chem. Soc. 2000, 122, 3534; e) B. M. Trost, M. K. Brennan, Org.
Lett. 2007, 9, 3961; f) F. Benfatti, G. Cardillo, L. Gentilucci, E. Mosconi,
A. Tolomelli, Org. Lett. 2008, 10, 2425; g) X. Wang, P. Guo, Z. Han, X.
Wang, Z. Wang, K. Ding, J. Am. Chem. Soc. 2014, 136, 405.
[8]
[9]
For a MBH-type reaction via metal catalysis and organomediation, see:
Y.-Q. Li, H.-J. Wang, Z.-Z. Huang, J. Org. Chem. 2016, 81, 4429.
a) G. Zhan, M.-L. Shi, Q. He, W.-J. Lin, Q. Ouyang, W. Du, Y.-C. Chen,
Angew. Chem. Int. Ed. 2016, 55, 2147; Angew. Chem. 2016, 128, 2187;
b) K.-K. Wang, P. Wang, Q. Ouyang, W. Du, Y.-C. Chen, Chem.
Commun. 2016, 52, 11104; c) for other examples, see: d) Y.-L. Liu, X.
Wang, Y.-L. Zhao, F. Zhu, X.-P. Zeng, L. Chen, C.-H. Wang, X.-L. Zhao,
J. Zhou, Angew. Chem. Int. Ed. 2013, 52, 13735; Angew. Chem. 2013,
125, 13980; d) F. Zhong, X. Han, Y. Wang, Y. Lu, Angew. Chem. Int. Ed.
2011, 50, 7837; Angew. Chem. 2011, 123, 7983; e) B. Tan, N. R.
Candeias, C. F. Barbas III, J. Am. Chem. Soc. 2011, 133, 4672; f) L.
Zhang, H. Liu, G. Qiao, Z. Hou, Y. Liu, Y. Xiao, H. Guo, J. Am. Chem.
Soc. 2015, 137, 4316.
Acknowledgements ((optional))
[10] Z.-C. Chen, P. Chen, Z. Chen, Q. Ouyang, H.-P. Liang, W. Du, Y.-C.
Chen, Org. Lett. 2018, 20, 6279.
We are grateful for the financial support from the NSFC
(21572135) and Sichuan University (2018SCUH0058).
[11] Unfortunately, the MBH carbonates from benzaldehyde readily
generated -allylpalladium species with Pd(PPh3)4, finally giving -regio-
selective O-alkylation products. See the SI and ref 7 for more details.
Keywords: auto-tandem catalysis • cooperative catalysis •
palladium catalysis • Lewis base catalysis •
MoritaBaylisHillman carbonate
[12] The structure of racemic 3o (CCDC 1882576) was confirmed by X-ray
analysis. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[13] For more details, see the Supporting Information.
[1]
[2]
For selected reviews of tandem reactions, see: a) L. F. Tietze, Chem.
Rev. 1996, 96, 115; b) S. F. Mayer, W. Kroutil, K. Faber, Chem. Soc. Rev.
2001, 30, 332; c) A. J. McCarroll, J. C. Walton, Angew. Chem. Int. Ed.
2001, 40, 2224; Angew. Chem. 2001, 113, 2282; d) K. C. Nicolaou, D. J.
Edmonds, P. G. Bulger, Angew. Chem. Int. Ed. 2006, 45, 7134; Angew.
Chem. 2006, 118, 7292; e) H. Pellissier, Chem. Rev. 2013, 113, 442; e)
X. Zeng, Chem. Rev. 2013, 113, 6864.
[14] Phosphonium salts have been used as pseudohalides in metal-catalyzed
coupling reactions. See: a) M. Sakamoto, I. Shimizu, A. Yamamoto,
Chem. Lett. 1995, 1101; b) L. K. Hwang, Y. Na, J. Lee, Y. Do, S. Chang,
Angew. Chem. Int. Ed. 2005, 44, 6166; Angew. Chem. 2005, 117, 6322;
c) X. Zhang, A. McNally, Angew. Chem. Int. Ed. 2017, 56, 9833; Angew.
Chem. 2017, 129, 9965; d) for a review, see: L. Wang, H. Chen, Z. Duan,
Chem. Asian J. 2018, 13, 2164.
For selected reviews, see: a) J.-C. Wasilke, S. J. Obrey, R. T. Baker, G.
C. Bazan, Chem. Rev. 2005, 105, 1001; b) A. Galván, F. J. Fañanás, F.
Rodríguez, Eur. J. Inorg. Chem. 2016, 2016, 1306.
This article is protected by copyright. All rights reserved.

10.1002/anie.201814403
Angewandte Chemie International Edition
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
Author(s), Corresponding Author(s)*
Page No. – Page No.
Title
((Insert TOC Graphic here))
Layout 2:
COMMUNICATION
Peng Chen, Zhi-Chao Chen, Yue, Li, Qin
Ouyang, Wei Du,* and Ying-Chun Chen*
Page No. – Page No.
Auto-Tandem Cooperative Catalysis
Using Phosphine/Palladium: Reaction
of MoritaBaylisHillman Carbonates
and Allylic Alcohols
ATCC: The chemoseletive activations of MoritaBaylisHillman carbonates from isatins and allylic carbonates are realized with simple
Pd(PPh3)4 precursor, through generating allylic phosphorus-ylides and -allylpalladium complexes, respectively. After the cooperative catalytic
-regioselective allylic alkylation reaction, the resulting alkene-phosphonium groups undergo Heck coupling to give spirooxindoles, furnishing a
[3+2] annulation reaction via unprecedented auto-tandem cooperative catalysis (ATCC).
This article is protected by copyright. All rights reserved.