Palladium-Catalyzed Desulfitative Cross-Coupling Reaction of Sodium Sulfinates with Propargylic Carbonates

Article abstract of DOI:10.1002/adsc.201900698

Desulfitative cross-coupling of propargylic carbonates with sodium sulfinates has been observed. The reaction exhibited good functional group compatibility affording allenes as a single product. Potential anticancer activities of these allene products were also studied. (Figure presented.).

Full text of DOI:10.1002/adsc.201900698

Title: Palladium-Catalyzed Desulfitative Cross-Coupling Reaction of
Sodium Sulfinates with Propargylic Carbonates
Authors: Anni Qin, Guirong Zhu, Qin Chen, Hui Qian, and Shengming
Ma
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: Adv. Synth. Catal. 10.1002/adsc.201900698
Link to VoR: http://dx.doi.org/10.1002/adsc.201900698

10.1002/adsc.201900698
Advanced Synthesis & Catalysis
Very Important Publication
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Palladium-Catalyzed Desulfitative Cross-Coupling Reaction of
Sodium Sulfinates with Propargylic Carbonates
Anni Qin, a Guirong Zhu, a Qin Chen,* a Hui Qian,* a and Shengming Ma* a,b
a
Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan
Lu, Shanghai 200433, P. R. China
E-mail: chenq@fudan.edu.cn; qian_hui@fudan.edu.cn; masm@sioc.ac.cn
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 345 Lingling Lu, Shanghai 200032, P. R. China
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Received: ((will be filled in by the editorial staff))
in which sodium arylsulfinates are used in the coupling
carbonates with sodium sulfinates has been observed. The reaction with propargylic carbonates to afford allenes
Abstract. Desulfitative cross-coupling of propargylic
reaction exhibited good functional group compatibility
affording allenes as a single product. Potential anticancer
activities of these allene products were also studied.
(Scheme 1d). The developed methodology discussed
in this manuscript offered a new alternative for
arylation due to the advantages, such as remarkable
stability, easy-handiness for workup, low cost, and
simple preparation from their corresponding sulfonyl
chlorides.
Keywords: Desulfitative; Cross-Coupling; Sodium
Sulfinates; Allenes
Scheme 1. Transition metal-catalyzed coupling reactions
with sodium sulfinates
Transition metal-catalyzed cross-coupling reaction-
s are important methodologies in organic synthesis.[1]
In particular, palladium-catalyzed carbon-carbon and
carbon-heteroatom bonds formation have been widely
used in the construction of natural products and
biologically active molecules.[2] Recently, much
attention has been paid to the desulfitative coupling for
the construction of C-C bonds from sodium
arylsulfinates, which were frequently used for
sulfonylation and sulfuration reactions (Scheme 1a).[3]
Sodium arylsulfinates are also used as aryl donors to
react with alkenes,[4] alkynes,[5] heteroarenes,[6] benzyl
chlorides,[7] aryl triflates,[8] nitriles,[9] and so on.[10] In
2003, Deng and co-workers reported a palladium-
catalyzed desulfitative hydroarylation of alkynes with
good regio- and stereoselectivity (Scheme 1b).[5a]
Later, Jiang and co-workers described an efficient
palladium-catalyzed coupling of sodium sulfinates and
alkynes for the selective synthesis of vinyl sulfones
and unsymmetrical internal alkynes (Scheme 1c).[5b]
Allenes are useful building blocks for the synthesis
of pharmaceuticals, natural products, and functional
materials.[11,12] Some methods toward efficient
synthesis of different types of allenes have been
successfully developed.[13] Transition metal-catalyzed
coupling of propargylic compounds with organo-
metallic reagents[14] such as organoboronic reagents,
[15] Grignard reagents,[16] and organozinc reagents[17] is
one of the most useful and efficient methodology to
synthesize allenes.[18] However, some organometallic
reagents are unstable, expensive, and toxic. To the best
of our knowledge, there is no literature reported to date
We began the study with propargylic carbonate 1a
and sodium p-toluenesulfinate 2a as the model
substrates to identify the best ligand for the reaction at
50 oC (Table 1). Triphenylphosphine (L1) was initially
employed as the ligand but the desired desulfitative
product allene 5aa was not formed. Instead, 4% of 1,2-
allenyl sulfone 3aa and 53% of propargylic sulfone
4aa were observed (Entry 1). Tri(o-tolyl)phosphine
(L2) did not give any products. Tri(m-tolyl)phosphine
(L3) and tri(p-tolyl)phosphine (L4) also preferred to
give sulfone 4aa as the major product (Entries 3 and
4).
Electron-deficient
ligand,
tris[3,5-
bis(trifluoromethyl)phenyl]phosphine L5, failed to
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900698
Advanced Synthesis & Catalysis
give the desired product (Entry 5). We were pleased to
efficiency when Ar group was biphenyl (5la) or
naphthyl (5ma).
find
the
electron-rich
ligand,
tris[2,6-
bis(methoxy)phenyl]phosphine (L6), could afford the
desulfitative allene product 5aa in 56% yield with an
excellent selectivity (Entry 6). The more electron-rich
ligand tris[2,4,6-(trimethoxy)phenyl]phosphine (L7)
also offered single product 5aa, however, the yield
was lower (27%, entry 7). Tri(cyclohexyl) phosphine
(L8) failed to give any products (Entry 8).
Table 2. Further optimization of reaction parametersa
T
MMR yield Recovery
Entry
[Pd]
solvent
t (h)
(oC)
of 5aa
(
%
)
of 1a (%)
Table 1. Ligand Screeninga
1
2
3
4
5
6
Pd2(dba)3•CHCl3 Toluene 50 19
Pd2(dba)3•CHCl3 Dioxane 50 19
56
23
35
71
70
10
69
22
12
76
9
Pd2(dba)3•CHCl3 DCE
Pd2(dba)3•CHCl3 DMF
Pd2(dba)3•CHCl3 MeCN
Pd2(dba)3•CHCl3 THF
50 19
50 19
trace
21
50
19
13
Yield (%)
3aa 4aa 5aa
Entry
R
3
/
4
/
5
Recovery (%)
50 19
62
7b Pd2(dba)3•CHCl3 Toluene 60 40
71
1
2
3
4
5
6
Ph (L1
)
4
/
53
/
/
/
1:13.2:/
N/A
trace
80
8b
9b
Pd(OAc)2
Pd2(dba)3
Toluene 60 42
Toluene 60 42
11
2-MeC6H4 (L2
3-MeC6H4 (L3
4-MeC6H4 (L4
)
)
)
60
5
51
/
1:10:/
1:13.2:/
N/A
trace
trace
72
10b
[Pd(allyl)Cl]2 Toluene 60 42.5
81
7
11 52
/
a)
3,5-(CF3)2C6H3 (L5)
/
/
/
/
/
Reaction conditions: 1a (0.2 mmol), 2a (0.3 mmol), [Pd] (5 mol%), L6 (12
mol%) in anhydrous toluene (1.0 mL). The yield of 5aa was determined by 1H
NMR analysis. b) 2a (1.05 equiv).
2,6-(MeO)2C6H3 (L6
)
56
/:/:1
35
2,4,6-(MeO)3C6H2
7
/
/
/
/
27
/
/:/:1
N/A
56
(
L7
)
Table 3. Scope of propargylic carbonatesa
8
Cy (L8
)
quant.
a)
Reaction conditions: 1a (0.2 mmol), 2a (0.3 mmol), Pd2(dba)3·CHCl3 (5
o
mol%), PR3 (12 mol%) in anhydrous toluene (1.0 mL) was stirred at 50 C for
19 h. The yields of 3aa, 4aa and 5aa were determined by 1H NMR analysis.
Among the solvents surveyed, the reaction in
dioxane resulted in 23% yield (Table 2, entry 2). While
no better results was observed in DCE, DMF, and
MeCN (Table 2, entries 3-5). The yield was slightly
improved to 62% when THF was used as solvent with
22% recovery of 1a (Table 2, entry 6). The yield of
5aa was improved to 71% with the reaction being
Entry
Ar, 1
Yield of 5 (%)
1
2
Ph (1a)
4-FC6H4 (1b)
78 (5aa)
72 (5ba)
72 (5ca)
70 (5da)
73 (5sa)
60 (5ta)
86 (5ea)
73 (5fa)
70 (5ga)
77 (5ha)
71 (5ia)
68 (5ja)
65 (5ka)
69 (5la)
69 (5ma)
3
4-ClC6H4 (1c)
4-BrC6H4 (1d)
3-BrC6H4 (1s)
2-BrC6H4 (1t)
4b
5b
6b,c
7
o
conducted at 60 C (Table 2, entry 7). After further
screening of palladium catalysts, we found
[Pd(allyl)Cl]2 was the most efficient, yielding 81% of
5aa (Table 2, entry 10). Thus, optimal conditions have
been defined as 5 mol% of [Pd(allyl)Cl]2 and 12 mol%
of L6 in toluene at 60 oC under N2 atmosphere.
3-MeOC6H4 (1e)
4-MeO2CC6H4 (1f)
4-NCC6H4 (1g)
2-MeC6H4 (1h)
3-MeC6H4 (1i)
4-MeC6H4 (1j)
2-MeO2COC6H4 (1k)
4-PhC6H4 (1l)
8 b
9
10
11
12
13
14
15
With the optimal reaction conditions in hand, we
next examined the scope of the desulfitative coupling
process. As shown in Table 3, a wide range of
propargylic carbonates with different substituents at
different positions reacted smoothly with sodium p-
toluenesulfinate 2a forming the corresponding allene
products with decent yields. The reaction is amenable
to both electron-withdrawing and electron-donating
aryl groups. Various functional groups, including
halides (5ba, 5ca, 5da, 5sa, and 5ta), ester (5fa),
cyano (5ga), and carbonate (5ka) are well tolerated in
the 2-alkynylic carbonates. There is no obvious
influence of the steric effect since substrates bearing
the methyl group at the o-, m-, and p-position of the
phenyl group all afforded the desired products with
good yields (5ha, 5ia, and 5ja). The reaction also
afforded corresponding allene products with good
1-Naphthyl (1m)
a)
Reaction conditions: 1 (0.2 mmol), 2a (0.21 mmol), [Pd(allyl)Cl]2 (5 mol %),
L6 (12 mol %), and toluene (1 mL) at 60 oC for 48 h, yield for isolated products.
b) [Pd(allyl)Cl]2 (10 mol %) and L6 (24 mol %) were used. c) 21% of 1t recovery
by using 14 μL CH2Br2 as internal standard.
Next, we turned our attention to the scope of the R1
group (Table 4). Alkyl groups with different functional
groups, such as halide (5na), cyano (5pa), and silyl-
protected alcohol (5qa) were well tolerated in this
transformation. Not only secondary propargylic
carbonates, tertiary propargylic carbonate 1r was also
working well affording the corresponding
tetrasubstituted allene 5ra. Sodium p-fluorosulfinate
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900698
Advanced Synthesis & Catalysis
2b reacted smoothly affording allene product 5ab with
78% yield. Finally, sodium 1-naphthylsulfinate 2c
could also work to afford 5ac in 82% yield.
intermediate II would afford intermediate III.
Subsequent reductive elimination would furnish the
product 5aa and regenerate the catalytically active
palladium(0) catalyst.
Scheme 2. Proposed Mechanism
Table 4. Scope of propargylic carbonates with sodium
sulfinatesa
(Ra)-
1
Yield
of
(%)
Entry
Ar
5
R1
R2
Ph H (1n
Ph H (1o
R3
67
1b
2c
3d
4
-(CH2)4Cl
-(CH2)2iPr
)
Tol (2a
Tol (2a
Tol (2a
Tol (2a
)
)
)
)
(
5na
)
73
)
(
5oa
)
56
-(CH2)3CN
-(CH2)3OTBS
nC6H13
Ph H (1p
Ph H (1q
)
)
(
(
5pa
)
)
73
5qa
CH
CH3
(1r)
59
(5ra)
Finally, we were intrigued by the potential
biological activities of these newly synthesized allene
products, so their cytotoxicities against A549 human
lung cancer cells were measured by using the
sulforhodamine B (SRB) assay. As shown in Figure
1A, most of the tested compounds significantly
inhibited
5e,f
6
Tol (2a)
3
78
5ab)
nBu
Ph H (1a
Ph H (1a
)
)
4-FC6H4 (2b)
(
1-Naphthyl
82
(5ac)
7g
nBu
(
2c
)
a)
Reaction conditions: 1 (0.2 mmol), 2 (0.21 mmol), [Pd(allyl)Cl]2 (5 mol %),
L6 (12 mol %), and toluene (1 mL) at 60 oC for 48 h, yield for isolated products.
b) The reaction time is 48.7 h. c) The reaction time is 66 h. d) The reaction time is
e)
54 h. Reaction at 80 oC. f) 17% of 1r recovery by using 14 μL CH2Br2 as
internal standard. g) 2c (2.0 equiv).
To gain further insight into the mechanism, we
carried out some control experiments. First, we set up
a reaction without any ligand and 96% of 1a was
recovered without forming any desired product (eq. 1).
The result suggests that the ligand L6 plays an
important role in this process for both the reactivity
and selectivity. When the normal coupling product
sulfone 6 was subjected to the standard conditions, no
desulfitative product 5aa was observed, indicating
sulfone 6 was not the intermediate (eq. 2).
A possible mechanism is proposed in Scheme 2.
Pd(0) would undergo SN2’-type oxidative addition
with propargylic carbonate 1a to give the allenylic
palladium methoxide intermediate I, which would
undergo ligand exchange with the sodium sulfinate 2a
to form the intermediate II. Desulfitation of
Figure 1. A) Cytotoxicity against A549 human lung cancer
cells; B) 5ka inhibited the proliferation of A549 cells in a
dose-dependent manner.
3
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900698
Advanced Synthesis & Catalysis
the growth of A549 cells at 100 μM. Among them, 5ka
showed the most potent activity with an IC50 of 28.27
μM (Figure 1B).
[3] a) K. Yuan, J. F. Soulꢀ, H. Doucet, ACS Catal. 2015, 5,
978-991. b) D. K. Ortgies, A. Hassanpour, F. Chen, S. Woo,
P. Forgione, Eur. J. Org. Chem. 2016, 405.
[4] a) X. Zhou, J. Luo, J. Liu, S. Peng, G.-J. Deng, Org. Lett.
2011, 13, 1432-1435. b) N. Taniguchi, Synlett 2013, 24,
2571-2574. c) J. Liao, Z. Zhang, X. Tang, W. Wu, W. Guo,
H. Jiang, J. Org. Chem. 2015, 80, 8903-8909. d) H. Wang,
Y. Li, R. Zhang, K. Jin, D. Zhao, C. Duan, J. Org. Chem.
2012, 77, 4849-4853.
[5] a) S. Liu, Y. Bai, X. Cao, F. Xiao, G.-J. Deng, Chem.
Commun. 2013, 49, 7501-7503. b) Y. Xu, J. Zhao, X. Tang,
W. Wu, H. Jiang, Adv. Synth. Catal. 2014, 356, 2029-2039.
[6] a) R. Chen, S. Liu, X. Liu, L. Yang, G.-J. Deng, Org.
Biomol. Chem. 2011, 9, 7675-7679. b) M. Wu, J. Luo, F.
Xiao, S. Zhang, G.-J. Deng, H.-A. Luo, Adv. Synth. Catal.
2012, 354, 335-340. c) M. Wang, D. Li, W. Zhou, L. Wang,
Tetrahedron 2012, 68, 1926-1930. d) B. Liu, Q. Guo, Y.
Cheng, J. Lan, J. You, Chem. Eur. J. 2011, 17, 13415-13419.
[7] F. Zhao, Q. Tan, F. Xiao, S. Zhang, G.-J. Deng, Org. Lett.
2013, 15, 1520-1523.
In summary, we have developed a new approach,
i.e., desulfitative coupling of sodium sulfinates with
propargylic carbonates, for the synthesis of allenes.
Excellent selectivity was achieved by using an
electron-rich and bulky phosphine ligand. The reaction
exhibits good substrate scope and functional group
compatibility. A preliminary biological study found
that some of these allene products exhibited significant
anticancer activity. Further studies related to this topic
are in progress in our laboratory.
[8] C. Zhou, Q. Liu, Y. Li, R. Zhang, X. Fu, C. Duan, J. Org.
Chem. 2012, 77, 10468-10472.
[9] a) M. Behrends, J. Sävmarker, P. J. R. Sjöberg, M.
Larhed, ACS Catal. 2011, 1, 1455-1459. b) J. Liu, X. Zhou,
H. Rao, F. Xiao, C.-J. Li, G.-J. Deng, Chem. Eur. J. 2011,
17, 7996-7999.
Experimental Section
General
Procedure
for
Palladium-Catalyzed
Desulfitative Cross-Coupling Reaction of Sodium
Sulfinates with Propargylic Carbonates
[10] For other selected examples, see: a) H. Rao, L. Yang,
Q. Shuai, C.-J. Li, Adv. Synth. Catal. 2011, 353, 1701-1706.
b) T. Miao, L. Wang, Adv. Synth. Catal. 2014, 356, 429-436.
c) J. Shi, X.-D. Tang, Y.-C. Wu, H.-N. Li, L.-J. Song, Z.-Y.
Wang, Eur. J. Org. Chem. 2015, 1193-1197. d) Y. Li, W.
Yang, G. Cheng, D. Yang, J. Org. Chem. 2016, 81, 4744-
4750.
[11] For a most recent monograph, see: Modern Allene
Chemistry, ed. N. Krause, A. S. K. Hashmi, Wiley-VCH,
Weinheim, 2004, vols 1 and 2.
[12] For selected reviews, see: a) F. López, J. L. Mascareñas,
Chem. Soc. Rev. 2014, 43, 2904-2915. b) J. Ye, S. Ma, Acc.
Chem. Res. 2014, 47, 989-1000. c) T. Lu, Z. Lu, Z.-X. Ma,
Y. Zhang, R. P. Hsung, Chem. Rev. 2013, 113, 4862-4904.
d) S. Yu, S. Ma, Angew. Chem. Int. Ed. 2012, 51, 3074-3112.
e) S. Ma, Acc. Chem. Res. 2009, 42, 1679-1688. f) M.
Brasholz, H.-U. Reissig, R. Zimmer, Acc. Chem. Res. 2009,
42, 45-56. g) S. Ma, Aldrichimica Acta 2007, 40, 91-102. h)
S. Ma, Chem. Rev. 2005, 105, 2829-2871. i) A. Hoffmann-
Röder, N. Krause, Angew. Chem. Int. Ed. 2004, 43, 1196-
1216. j) L. K. Sydnes, Chem. Rev. 2003, 103, 1133-1150. k)
S. Ma, Acc. Chem. Res. 2003, 36, 701-712.
To an oven-dried 4 mL vial were added [Pd(allyl)Cl]2 (3.6
mg, 0.01 mmol), L6 (10.6 mg, 0.024 mmol), TolSO2Na
(37.8 mg, 0.21 mmol), 1a (49.1 mg, 0.2 mmol), and
anhydrous toluene (1 mL) under the N2 atmosphere. The
vial was capped and the resulting mixture was stirred at 60
oC for 48 h in reaction block. The reaction mixture was
filtered through a short column of silica gel (3.5 cm) eluted
with ethyl acetate (13 mL), and concentrated. The residue
was purified by column chromatography on silica gel to
afford 5aa.
Acknowledgements
Financial support from the National Natural Science
Foundation of China (Grant No. 21690063) and Shanghai
Sailing Program (18YF1402000) is greatly appreciated. Mr
Liu Qi in this group for reproducing the results for 5ha, 5oa
and 5ra as presented in this study.
References
[13] For reviews on the synthesis of allenes, see: a) Chapters
1–8 in ref. 11. b) R. K. Neff, D. E. Frantz, ACS Catal. 2014,
4, 519-528. c) S. Yu, S. Ma, Chem. Commun. 2011, 47,
5384-5418. d) M. Ogasawara, Tetrahedron: Asymmetry
2009, 20, 259-271. e) K. M. Brummond, J. E. DeForrest,
Synthesis 2007, 6, 795-818. f) G. B. Hammond, ACS Symp.
Ser. 2005, 911, 204-215. g) N. Krause, A. Hoffmann-Röder,
Tetrahedron 2004, 60, 11671-11694.
[14] For reviews, see: a) S. Ma, Eur. J. Org. Chem. 2004,
1175-1183. b) C. Bruneau, C. Darcel, P. H. Dixneuf, Curr.
Org. Chem. 1997, 1, 197-218.
[15] a) T. Moriya, N. Miyaura, A. Suzuki, Synlett 1994, 149-
151. b) M. Ishikura, I. Agata, Heterocycles 1996, 43, 1591-
1595. c) M. Ishikura, Y. Matsuzaki, I. Agata, N. Katagiri,
[1] a) Metal-Catalyzed Cross-Coupling Reactions, ed. F.
Diederich, P. J. Stang, Wiley-VCH, New York, 1998. b) J.
K. Stille, Angew. Chem. Int. Ed. 1986, 25, 508-524. c) N.
Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457-2483. d) X.
Chen, K. M. Engle, D. Wang, J. Yu, Angew. Chem. Int. Ed.
2009, 48, 5094-5115. e) H. Motohashi, K. Mikami, Org.
Lett. 2018, 20, 5340-5343.
[2] a) J. F. Hartwig, Acc. Chem. Res. 1998, 31, 852-860. b)
T. Kondo, T. Mitsudo, Chem. Rev. 2000, 100, 3205-3220. c)
E. M. Beccalli, G. Broggini, M. Martinelli, S. Sottocornola,
Chem. Rev. 2007, 107, 5318-5365.
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900698
Advanced Synthesis & Catalysis
Tetrahedron 1998, 54, 13929-13942. d) M. Murakami, H.
Igawad, Helv. Chim. Acta. 2002, 85, 4182-4188. e) M.
Yoshida, T. Gotou, M. Ihara, Tetrahedron Lett. 2004, 45,
5573-5575. f) M. Yoshida, H. Ueda, M. Ihara, Tetrahedron
Lett. 2005, 46, 6705-6708. g) G. A. Molander, E. M.
Sommers, S. R. Baker, J. Org. Chem. 2006, 71, 1563-1568.
h) M. Yoshida, T. Okada, K. Shishido, Tetrahedron 2007,
63, 6996-7002. i) C. Wang, L. Kong, Y. Li, Y. Li, Eur. J.
Org. Chem. 2014, 3556-3560. j) H. Luo, Y. Yu, S. Ma, Org.
Chem. Front. 2016, 3, 1705-1710. k) J Ruchti, E. M.
Carreira, Org. Lett. 2016, 18, 2174−2176. l) Y. Yao, G. Zhu,
Q. Chen, H. Qian, S. Ma, Org. Chem. Front. 2019, 6, 304-
308. m) J. Xiao, H. Luo, S. Huang, H. Qian, S. Ma, Chem.
Commun. 2018, 54, 10451-10454.
[18] For other organometallic reagents, selected examples
see: a) E. Keinan, E. Bosch, J. Org. Chem. 1986, 51, 4006-
4016. b) Q.-H. Li, J.-Y. Jeng, H.-M. Gau, Eur. J. Org. Chem.
2014, 7916-7923. c) R. Riveiros, D. Rodríguez, J. P. Sestelo,
L. A. Sarandeses, Org. Lett. 2006, 8, 1403-1406. d) R.
Riveiros, J. P. Sestelo, L. A. Sarandeses, Synthesis 2007, 22,
3595-3598. e) K. Tsutsumi, S. Ogoshi, K. Kakiuchi, S.
Nishiguchi, H. Kurosawa, Inorg. Chim. Acta 1999, 296, 37-
44. For
a
recent report on Palladium-catalyzed
decarboxylative arylation for allene synthesis, see: (f) I.
Scheipers, C. Mück-Lichtenfeld, A. Studer, Angew. Chem.
Int. Ed. 2019, 58, 6545-6548.
[16] a) T. Jeffery-Luong, G. Linstrumelle, Tetrahedron Lett.
1980, 21, 5019-5020. b) K. Ruitenberg, H. Kleijin, H.
Westmijze, J. Meijer, P. Vermeer, Recl. Trav. Chim. Pays-
Bas 1982, 101, 405-409.
[17] a) K. Ruitenberg, H. Kleijn, C. J. Elsevier, J. Meijer, P.
Vermeer, Tetrahedron Lett. 1981, 22, 1451-1452. b) H.
Kleijin, J. Meijer, G. C. Overbeek, P. Vermeer, Recl. Trav.
Chim. Pays-Bas 1982, 101, 97-101. c) C. J. Elsevier, P. M.
Stehouwer, H. Westmijze, P. Vermeer, J. Org. Chem. 1983,
48, 1103-1105. d) P. H. Dixneuf, T. Guyot, M. D. Ness, S.
M. Roberts, Chem. Commun. 1997, 0, 2083-2084. e) T.
Kunno, M. Tanikawa, T. Ishihara, H. Yamanaka, Chem. Lett.
2000, 29, 1360-1361. f) S. Ma, G. Wang, Angew. Chem. Int.
Ed. 2003, 42, 4215-4217.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900698
Advanced Synthesis & Catalysis
COMMUNICATION
Palladium-Catalyzed Desulfitative Cross-Coupling
Reaction of Sodium Sulfinates with Propargylic
Carbonates
Adv. Synth. Catal. Year, Volume, Page – Page
A. Qin, G. Zhu, Q. Chen*, H. Qian*, S. Ma*
6
This article is protected by copyright. All rights reserved.