Efficient access to 1,4-benzothiazine: Palladium-catalyzed double C-S bond formation using Na2S2O3 as sulfurating reagent

DOI: 10.1021/ol400618k

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Organic Letters p. 2594 - 2597 (2013)

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Qiao, Zongjun

Liu, Hui

Xiao, Xiao

Fu, Yana

Wei, Jianpeng

Li, Yuxue

Jiang, Xuefeng

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Article abstract of DOI:10.1021/ol400618k

A novel Pd-catalyzed double C-S bond formation coupling reaction has been developed. This protocol, in which Na₂S₂O₃ was used as sulfurating reagent in metal-catalyzed reactions, provides an efficient method for the synthe

Full text of DOI:10.1021/ol400618k

ORGANIC

LETTERS

2013

Vol. 15, No. 11

2594–2597

Efficient Access to 1,4-Benzothiazine:

Palladium-Catalyzed Double CꢀS Bond

Formation Using Na₂S₂O₃as Sulfurating

Reagent

Zongjun Qiao,^†,§Hui Liu,^†,§Xiao Xiao,^†Yana Fu,^†Jianpeng Wei,^†Yuxue Li,^‡and

Xuefeng Jiang*^,†

Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of

Chemistry, East China Normal University, 3663 North Zhongshan Road, Shanghai

200062, P. R. China, and State Key Laboratory of Organometallic Chemistry, Shanghai

Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu,

Shanghai 200032, P.R. China

xfjiang@chem.ecnu.edu.cn

Received March 7, 2013

ABSTRACT

A novel Pd-catalyzed double CꢀS bond formation coupling reaction has been developed. This protocol, in which Na₂S₂O₃was used as sulfurating

reagent in metal-catalyzed reactions, provides an efficient method for the synthesis of substituted 1,4-benzothiazine derivates, which are

structural elements of numerous bioactivity molecules rendering this protocol attractive to both synthetic and medicinal chemistry.

Organosulfur heterocycles, standing for an important

class of biological organic compounds, have been widely

used as pharmaceuticals, functional materials, and

synthetic intermediates.¹1,4-Benzothiazine derivatives

are well-known to display diverse biological activities in

vivo and in vitro, such as antibacterial,²antidiabetic,³

antiarrhythmic,⁴antitumor,⁵and neurodegenerative diseases

(Parkinson’s disease and Alzheimer’s disease).⁶On the basis

of a broad spectrum of important pharmaceutically active

compounds and natural products (Figure 1), 1,4-benzothia-

zine derivatives have triggered sustainably increasing atten-

tion in the synthetic and medicinal chemistry communities.

Due to the significance of organosulfur compounds,

the development of new and efficient methods for the

incorporation of sulfur into organic frameworks is today

an important and challenging task. Compared to the

construction of CꢀN and CꢀO bonds by transmetal-

catalyzed cross-coupling, CꢀS bond formation has been

less studied due to deactivation of the metal catalysts by

the strong coordinating properties of sulfur compounds

(Scheme 1).⁷In 1980, Migita and co-workers first reported

Dedicated to Professor Guo-Qiang Lin on the occasion of his 70th birthday.

^†East China Normal University.

^‡Chinese Academy of Sciences.

^§Z.Q. and H.L. contributed equally.

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Katritzky, A. R., Meth-Cohn, O., Rees, C. W., Eds.; Academic Press: London,

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Vigalok, A., Ed.; Springer: Heidelberg, 2010; Vol. 31, p 39.

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Pagella, P.; Palmioli, M.; Segre, G.; Terni, P. J. Med. Chem. 1987, 30,

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7658.

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10.1021/ol400618k

Published on Web 05/09/2013

2013 American Chemical Society

process. Therefore, the search for new sulfurating reagents

to apply to the construction of S-containing heterocycles

is an urgent need. Some elegant metal sulfides have

been developed recently for constructing organosulfur

molecules.¹⁶In 2009, Ma and co-workers reported the first

example for the use of Na₂S as sulfuration reagent.^16aIn

2011, a general method for the Pd-catalyzed Ar-SCF₃

bond-forming reaction using AgSCF₃was developed by

the Buchwald group.^16bThiourea as a thiol surrogate has

also been applied in the synthesis of sulfur-containing

molecules.¹⁷Ma et al. developed a novel thiiranation of

1,2-allenyl sulfones by using Na₂S₂O₃as sulfur source.¹⁸

However, to the best of our knowledge, Na₂S₂O₃as a

sulfurating reagent, which is readily available as stable salt

without any smell, is untouched in metal-catalyzed cou-

pling. Herein, we report a novel one-pot Pd-catalyzed

double CꢀS bond formation reaction using Na₂S₂O₃as

the sulfurating reagent.

Figure 1. Bioactive 1,4-benzothiazine scaffolds.

Scheme 1. Metal-Catalyzed CꢀS Bond Construction

the coupling of thiols and aryl halides catalyzed by Pd-

(PPh₃)₄.⁸A wide range of transition metals, such as Pd,⁹

Ni,¹⁰Co,¹¹In,¹²Cu,¹³Fe,¹⁴and Rh¹⁵have been developed

to achieve CꢀS bond formation. However, in most cases,

the thiols as the sulfur source are indispensable partners,

which generally suffer from preparation difficulties due to

the apt oxidation and unpleasant smell during the whole

Our study commenced with the reaction of 1aa (N-(2-

iodoethyl)-N-(2-iodophenyl)-4-methylbenzenesulfon-amide)

catalyzed by PdCl₂(dppf) in the presence of Na₂S₂O₃5H₂O.

Gratifyingly, the desired 4-tosyl-3,4-dihydro-2H-benzo[b]-

[1,4]thiazine 2a was isolated in 10% yield with 66% 1aa

recovered by using Cs₂CO₃as base in MeCN (Table 1,

entry 1). The structure of 2a was confirmed by X-ray

(7) (a) Hegedus, L. L.; McCabe, R. W. In Catalyst Poisoning; Marcel

Dekker: New York, 1984. (b) Hutton, A. T. In Comprehensive Coordination

Chemistry; Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon:

Oxford, 1984; Vol. 5, p 1151.

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Kosugi, M. Bull. Chem. Soc. Jpn. 1980, 53, 1385. (b) Kosugi, M.;

Shimizu, T.; Migita, T. Chem. Lett. 1978, 13.

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Guzei, I. A. J. Am. Chem. Soc. 1998, 120, 9205. (b) Murata, M.;

Buchwald, S. L. Tetrahedron 2004, 60, 7397. (c) Itoh, T.; Mase, T.

Org. Lett. 2004, 6, 4587. (d) Fernandez-Rodroeguez, M. A.; Shen, Q.;

Hartwig, J. F. J. Am. Chem. Soc. 2006, 128, 2180. (e) Itoh, T.; Mase, T.

Org. Lett. 2007, 9, 3687. (f) Lee, J. Y.; Lee, P. H. J. Org. Chem. 2008, 73,

7413. (g) Dahl, T.; Tornoe, C. W.; Bang-Andersen, B.; Nielsen, P.;

Jorgensen, M. Angew. Chem., Int. Ed. 2008, 47, 1726. (h) Eichman, C. C.;

Stambuli, J. P. J. Org. Chem. 2009, 74, 4005.

analysis.¹⁹To enhance the solubility of Na₂S₂O₃

5H₂O, H₂O was added as cosolvent which made a slight

improvement to the yield (Table 1, entry 2). It afforded a

20% yield when 5.0 equiv of Na₂S₂O₃5H₂O were used,

but too much Na₂S₂O₃5H₂O did not favor this transfor-

mation (Table 1, entries 3 and 4). Then phase-transfer

catalysts were tested and TBAB was proved to be a better

choice affording 39% yield (Table 1, entry 6). A great

(10) (a) Zhang, Y. G.; Ngeow, K. C.; Ying, J. Y. Org. Lett. 2007, 9,

3495. (b) Millois, C.; Diaz, P. Org. Lett. 2000, 2, 1705.

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T.; Moriya, T.; Ikeda, R.; Konakahara, T. Org. Lett. 2012, 14, 4366. (c)

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2002, 4, 2803. (b) Jammi, S.; Sakthivel, S.; Rout, L.; Mukherjee, T.;

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74, 1971. (c) Larsson, P. F.; Correa, A.; Carril, M.; Norrby, P. O.; Bolm,

C. Angew. Chem., Int. Ed. 2009, 48, 5691. (d) Xu, H.-J.; Zhao, Y.-Q.;

Feng, T.; Feng, Y.-S. J. Org. Chem. 2012, 77, 2878.

(16) (a) Ma, D.; Xie, S.; Xue, P.; Zhang, X.; Dong, J.; Jiang, Y.

Angew. Chem., Int. Ed. 2009, 48, 4222. (b) Teverovskiy, G.; Surry, D. S.;

Buchwald, S. L. Angew. Chem., Int. Ed. 2011, 50, 7312. (c) Ke, F.; Qu, Y.;

Jiang, Z.; Li, Z.; Wu, D.; Zhou, X. Org. Lett. 2011, 13, 454. (d) van den

Hoogenband, A.; Lange, J. W.; Bronger, R. P.; Stoit, A. R.; Tupstra,

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Tetrahedron Lett. 2007, 48, 3033.

ꢀꢀꢀ

(17) (a) Argu1ello, J. E.; Schmidt, L. C.; Penenory, A. B. Org. Lett.

2003, 5, 4133. (b) Firouzabadi, H.; Iranpoor, N.; Gholinejad, M. Adv.

Synth. Catal. 2010, 352, 119. (c) Kuhn, M.; Falk, F. C.; Paradies, J. Org.

Lett. 2011, 13, 4100.

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47, 2880. (b) Wu, J.-R.; Lin, C.-H.; Lee, C.-F. Chem. Commun. 2009,

4450. (c) Lin, Y.-Y.; Wang, Y.-J.; Lin, C.-H.; Cheng, J.-H.; Lee, C.-F.

J. Org. Chem. 2012, 77, 6100. (d) Wang, H.; Wang, L.; Shang, J.; Li, X.;

Wang, H.; Gui, J.; Lei, A. Chem. Commun. 2012, 48, 76.

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14, 5318. (b) Arisawa, M.; Suzuki, T.; Ishikawa, T.; Yamaguchi, M.

J. Am. Chem. Soc. 2008, 130, 12214. (c) Ajiki, K.; Hirano, M.; Tanaka,

K. Org. Lett. 2005, 7, 4193.

(18) Zhou, C.; Fu, C.; Ma, S. Angew. Chem., Int. Ed. 2007, 46, 4379.

(19) CCDC-917799 (2a): C₁₅H₁₅NO₂S₂, MW = 305.40, monoclinic,

space group P2(1)/n, final R indices [I > 2σ(I)], R1 = 0.0393, wR2 =

0.1131, R indices (all data), R1 = 0.0461, wR2 = 0.1187, a = 8.3042(5) A,

b= 8.0453(5) A,c= 22.1419(14) A,R=90°,β= 98.853(2)°,γ=90°,V=

1461.67(16) A , T = 296(2) K, Z = 4, reflections collected/unique: 119430/

3560 (R(int) = 0.0239). These data can be obtained free of charge from the

Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/

data_request/cif.

Org. Lett., Vol. 15, No. 11, 2013

2595

Table 1. Optimization of Pd-Catalyzed Double CꢀS Bond Formation^a

entry

[Pd]

ligand (mol %)

base

solvent

MeCN

additive

yield^b(%)

PdCl₂(dppf)

Pd(OAc)₂

Cs₂CO₃

Na₂CO₃

K₂CO₃

10^c

15^c

19^d

MeCN/H₂O (10:1)

MeCN/H₂O (5:1)

MeCN/H₂O (20:1)

TBAC

TBAB

TBAI

dppf (2)

dppf (5)

dppf (10)

dppf (5)

TFP (10)^e

Sphos (10)^f

PCy₃(10)^g

dppf (5)

TBAB

trace

Pd(dba)₂

Pd(PPh₃)₂Cl₂

PdCl₂(dppf)

Ag₂CO₃

Cs₂CO₃

complicated^h

complicatedⁱ

^aReaction conditions: 1aa (0.1 mmol), [Pd] (0.01 mmol), base (0.3 mmol), Na₂S₂O₃5H₂O (0.5 mmol), additive (0.03 mmol), solvent (2.0 mL),

150 °C, 6 h. ^bIsolated yield. ^cNa₂S₂O₃5H₂O (0.2 mmol, 2.0 equiv). ^dNa₂S₂O₃5H₂O (1.0 mmol, 10.0 equiv). ^eTFP = tri(2-furyl)phosphine.

^fSphos =2-dicyclohexylphosphino-2⁰,6⁰-dimethoxybiphenyl. ^gPCy₃= tricyclohexylphosphine. ^hReplace Na₂S₂O₃with S₈. ⁱReplace Na₂S₂O₃with Na₂S.

improvement was achieved by using additional 5 mol % of

dppf, which is thought to be stabilized the Pd inter-

mediate,²⁰and the yield was elevated to 78% (Table 1,

entries 8ꢀ10). Other Pd catalysts were tested, which gave

low efficiency, respectively (Table 1, entries 11ꢀ13). Dif-

ferent ligands and bases were also screened, which, however,

did not exhibit any superior performance than dppf and

Cs₂CO₃(Table 1, entries 14ꢀ19). Significantly, when MeCN:

H₂O (20:1) was used, the highest yield (96%) was achieved

(Table 1, entry 21). Neither S₈nor Na₂S could take the

integrant place of Na₂S₂O₃(Table 1, entries 22 and 23).

Under the optimized reaction conditions, we examined a

series of substrates to establish the scope of this methodol-

ogy shown in Table 1. Substrates bearing Csp³-I, Br, Cl,

OMs, and OTs on the saturated carbon could afford

good to excellent yields (Table 2, 2a). Fluoro and chloro

atoms are well-tolerated under the standard conditions with

90ꢀ94% yields (Table 2, 2b and 2c). The yield was reduced

to 46% with a bromo substitution at C4, which is sensitive

under these conditions (Table 2, 2d). Both electron-with-

drawing and electron-donating substitutions on the aro-

matic ring gave the corresponding products in good yields

(Table 2, 2eꢀl). It is worth noting that 2j with free alcohol

proceeds smoothly in 42% yield. 2k containing other sulfur

atom did not prevent the coupling reaction (Table 2, 2k).

Multisubstituted iodobenzene could also afford the desired

product in good yield (Table 2, 2m). Ns (4-Nitrobenzene-

sulfonyl) on nitrogen did not change the reactivity (Table 2,

2n). And not only the six-membered ring but also the seven-

and five-membered rings 2o and 2p could be obtained in

moderate yields. Carbon-tethered substrates could also af-

ford the desired products in good yields (Table 2, 2p and 2q).

As mentioned above, 1,4-benzothiazine derivates are

versatile intermediates and building blocks in organic

synthesis. When the Ts group was removed with 35%

HBr in HOAc in the presence of anisole,²¹2ab could be

efficiently transformed to 2a-2, which is the ion channel

antagonistic activity molecule (Scheme 2, 2a-2). Another

practical application was achieved through the hydro-

lysis of 2g to the 4-tosyl-3,4-dihydro-2H-benzo[b][1,4]-

thiazine-7-carboxylic acid 2gb, which is the key intermedi-

ate for the synthesis of antirheumatic agent MX-68.²²

4-Tosyl-3,4-dihydro-2H-benzo[b][1,4]-thiazine 2a could

be converted to sulfoxide by NaIO₄, which was an analo-

gue of rufloxacin. When compound 2a was subjected to

(21) Matsuoka, H.; Ohi, N.; Mihara, M.; Suzuki, H.; Miyamoto, K.;

Maruyama, N.; Tsuji, K.; Kato, N.; Akimoto, T.; Takeda, Y.; Yano, K.;

Kuroki, T. J. Med. Chem. 1997, 40, 105.

(22) Maruyama, N.; Shimizu, H.; Sugiyama, T.; Watanabe, M.;

Makino, M.; Kato, M.; Shimizu, M. Org. Process Res. Dev. 2004, 8, 883.

(20) Liu, H.; Qiao, Z.; Jiang, X. Org. Biomol. Chem. 2012, 10, 7274.

2596

Org. Lett., Vol. 15, No. 11, 2013

Scheme 2. Synthetic Transformation

product 2a was detected but the CꢀN bond cleavage

product 6 was found in 34% yield (eq 5). These evidence

indicated that sulfuration should not start from Csp³.

However, the reaction pathway was still unsharp.

Table 2. Pd-Catalyzed Double CꢀS Bond Formation^a

In conclusion, we have developed a novel method for the

synthesis of substituted 1,4-benzothiazine derivates which

relies on a Pd-catalyzed coupling reaction. The important

feature of this method is using stable Na₂S₂O₃salt as

sulfurating reagent which makes it free from foul-smelling

thiols. The successful application of Na₂S₂O₃as sulfur

source will stimulate studies on metal catalyzed CꢀS bond

formation by employing those inexpensive readily avail-

able reagents. The significance of the 1,4-benzothiazine

scaffold as a structural element should render this protocol

attractive for both synthetic and medicinal chemistry.

Na₂S₂O₃as sulfurating reagent in other useful natural

product syntheses is undergoing in our laboratory.

^aReaction conditions: 1 (0.1 mmol), PdCl₂(dppf) (0.01 mmol,

10 mol %), dppf (0.005 mmol, 5 mol %), Cs₂CO₃(0.3 mmol), Na_2-

S₂O₃5H₂O (0.5 mmol), TBAB (0.03 mmol, 30 mol %), MeCN:H₂O

(2.0 mL, 20:1), 8 h. ^bIsolated yield.

m-CPBA, sulfone 2ad was obtained efficiently, which is the

analogue of NorA multidrug efflux pump inhibitors.

To investigate that how the Na₂S₂O₃was introduced to

this system, some control experiments were tentatively

examined. Straightforward alkylated thiolsulfate inter-

mediate 3 via S_N2 replacement²³were proposed (eq 1).

However, no reaction was detected and coumpound 4 was

almost fully recovered (eq 2). When 1aa was tested without

PdCl₂(dppf)/dppf (eq 3) or Cs₂CO₃(eq 4), no intermediate

3 was formed. Another possible transformation was

that 3 was hydrolyzed to thiol 5 which might be converted

to 2a via Pd-catalyzed cross coupling. However, when

compound 5 was subjected to stardard conditions, no

Acknowledgment. Financial support was provided by

the NSFC (21272075), NCET(12-0178), the “Shanghai

Pujiang Program” (12PJ1402500), “Shanghai Talent Devel-

opment Support” (2011022), and CPSF (2012M520858).

Supporting Information Available. Experimental pro-

cedures and spectra for all previously unreported com-

pounds. This material is available free of charge via the

Internet at http://pubs.acs.org.

(23) Han, M.; Hara, M. J. Am. Chem. Soc. 2005, 127, 10951.

Org. Lett., Vol. 15, No. 11, 2013

The authors declare no competing financial interest.

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Article Doi

Efficient access to 1,4-benzothiazine: Palladium-catalyzed double C-S bond formation using Na2S2O3 as sulfurating reagent

DOI: 10.1021/ol400618k

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Article abstract of DOI:10.1021/ol400618k

Full text of DOI:10.1021/ol400618k

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