SPOTLIGHT

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Silver Carbonate
Compiled by Igor Dias Jurberg
Igor Dias Jurberg was born in 1984, in Rio de Janeiro, Brazil. He obtained his PhD from cole Polytechnique (20072010), Paris, under the supervision of Dr. Fabien Gagosz and Prof. Dr. Samir Zard, working on the synthesis of alkynes and new transformations catalyzed by gold(I) complexes. Since 2011, he is pursuing postdoctoral studies in the group of Dr. Nuno Maulide at the MaxPlanck-Institut fr Kohlenforschung, Mlheim an der Ruhr, working on the development of original pericyclic cascades and CH functionalization strategies. Max-Planck-Institut fr Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mlheim an der Ruhr, Germany E-mail: jurberg@mpi-muelheim.mpg.de

Spotlight 375
This feature focuses on a reagent chosen by a postgraduate, highlighting the uses and preparation of the reagent in current research

Introduction
Silver carbonate, Ag2CO3, is a odorless, yellow to yellowgrey powder poorly soluble in water. Upon heating, it gradually decomposes to silver oxide, Ag2O, and CO2 close to its melting point of 210 C. Silver carbonate is commercially available, but can also be readily accessed through the reaction of cheaper silver nitrate with sodium carbonate in water (Scheme 1).1
2 AgNO3 + Na2CO3 H2O, r.t. Ag2CO3 + 2 NaNO3

Ag2CO3

2 HNTf2

H2O, 65 C

2 AgNTf2

H2 O

CO2

Scheme 2 Silver carbonate can also be used for the preparation of other useful silver salts

Scheme 1 Silver carbonate is easily obtained from silver nitrate and sodium carbonate

Silver carbonate has found a myriad of different uses in organic chemistry, notably as oxidizing agent (Fetizons reagent), as catalyst for alkyne activation, as halogen scavenger and as base and/or oxidant of choice for various transition-metal-catalyzed reactions. Selected applications of silver carbonate in these diverse contexts will be presented here.

Silver carbonate can also be used to prepare other silver salts. One such salt, particularly useful in catalysis is sil-

Abstracts
(A) Oxidation of Alcohols: Fetizons reagent (silver carbonate on celite) is known to be a mild oxidizing agent capable of converting alcohols into aldehydes and ketones.3 Here, this reagent is applied in the complex setting of an enantioselective total synthesis of (+)-upial.4 The desired lactone was obtained from the corresponding lactol in excellent 94% yield.

CO2Me O 12 steps, 21% overall yield

Ag2CO3 on celite (5 equiv) H H O OH C6H6, 80 C H 94% H O O

two steps, 50% CHO H O O

(+)-upial

(B) 5-Exo-dig Cyclization of Alcohols and Carboxylic Acids: Alcohols containing a proximal acetylenic part5 and isoindolones containing g-acetylenic carboxylic acid moieties6 can be efficiently cyclized using a catalytic amount of Ag2CO3.

OH R

Ag2CO3 (0.10 equiv) C6H6, 80 C R

O racemic, 2 examples, 9099%5

O CO2H N R O Ag2CO3 (0.05 equiv) PhMe, 80 C O N R O

racemic, 7 examples, 74100%6

SYNLETT 2011, No. 20, pp 30533054xx. 201 Advanced online publication: 29.11.2011 DOI: 10.1055/s-0031-1290086; Art ID: V38211ST Georg Thieme Verlag Stuttgart New York

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ver bis(trifluoromethanesulfonyl)imide, derived from the reaction of silver carbonate and triflimide (Scheme 2).2

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(C) Halogen Scavenger; Generation of Nitrilimines: The azeto[3,4:2,3]pyrano[4,5-c]pyrazole skeleton holds potential interest as a b-lactamase-resistant antibiotic. An enantioselective route towards one member of this class was developed from the intramolecular [3+2] cycloaddition of a nitrilimine and a proximal alkene. The nitrilimine was generated via chlorine abstraction from the parent hydrazonoyl chloride using silver carbonate.7 (D) Halogen Scavenger; CH Oxidation Strategy: In landmark work,8 a CH oxidation strategy was employed for the synthesis of eudesmane terpenes. The syntheses of two of them, dihydroxyeudesmane and pygmol, feature as key steps the selective bromination of the more reactive tertiary carbon from the isopropyl sidechain, followed by a cyclization event assisted by silver carbonate. After hydrolysis of the cyclic carbonate formed, the corresponding diol is obtained in a very selective manner.

N NHPh Cl O N O PMP O
+

Ph Ph Ag2CO3 (2 equiv) O dioxane, r.t. N PMP

N N

N O H

Ph

Ph

Ph

N O PMP enantiopure, 60%

O +

O O

1) MeCO2Br (1 equiv) CH2Cl2, 0 C 2) sunlamp H

R CF3CH2

O O NH

Br

CF3CH2 NH R = H, 10 steps, 21% overall yield R = OH, 11 steps, 17% overal yield

Ag2CO3 (1.2 equiv), r.t.; then aq AcOH

R = H dihydroxyeudesmane 43% (+ 39% starting bicycle) R = OH pygmol R 52% (+ 30% starting bicycle)

LiOH (10 equiv) R HO enantiopure HO O O O

(E) Halogen Scavenger: Aziridinium Ion Formation: A chiral anion phase-transfer catalysis was established by taking advantage from the low solubility of silver carbonate and the generally high solubility of (S)-TRIP salts in organic solvents. Silver carbonate abstracts the chlorine atom to generate an aziridium phosphate ion pair,9 whose chiral anion directs the enantioselective nucleophilic aziridinium ring opening to afford the corresponding amino ethers in good yields and excellent enantioselectivities.10 (F) Base/Oxidant for Decarboxylative Cross-Coupling: An efficient, regio- and chemoselective palladium-catalyzed intramolecular arylation of benzoic acid derivatives by means of a decarboxylation/CH activation sequence using silver carbonate as base and oxidant of choice has been described.11 (G) Oxidant for OlefinationMichael Addition Sequence: The use of dinuclear rhodium species [Cp*RhCl2]2 as catalyst and Ag2CO3 as oxidant allows direct access to Heck cross-coupled products without the need for prior arene functionalization.12 The styrene product obtained undergoes spontaneous Michael addition under the reaction conditions to afford the corresponding cyclized products in good yields.13

Ph

Ph Cl R1 N (S)-TRIP (0.15 equiv) R OH (4 equiv), Ag2CO3 (0.6 equiv)

3

R1 N R2 O O * O O P

Ph

OR3 R1 N

Ph

4 MS, PhMe, 50 C

Ph

Ph

R2 racemic

R2 13 examples 5095% yield 9097% ee

CO2H R1 O R2 Pd(TFA)2 (0.15 equiv) Ag2CO3 (3 equiv) 5% DMSO1,4-dioxane 150 C R1 O 14 examples, 3985% R2

O R1 + N H Ar O [Cp*RhCl2]2 (0.04 equiv) R1 N H Ar R1

O N Ar EWG

Ag2CO3 (2 equiv) EWG MeCN, 110C (2 equiv) sealed tube

EWG

racemic 20 examples, 4595%

References
(1) For a detailed protocol see: Xu, C.; Liu, Y.; Huang, B.; Li, H.; Qin, X.; Zhang, X.; Dai, Y. Appl. Surf. Sci. 2011, 257, 8732. (2) For a detailed protocol see: Vij, A.; Zheng, Y.; Kirchmeier, R. L.; Shreeve, J. M. Inorg. Chem. 1994, 33, 3281. (3) Tojo, G.; Fernndez, M. Oxidation of Alcohols to Aldehydes and Ketones; Springer Science; Business Media: New York, 2006. (4) Takahashi, K.; Watanabe, M.; Honda, T. Angew. Chem. Int. Ed. 2008, 131. (5) Other examples using stoichiometric amounts of Ag2CO3 have also been reported: Pale, P.; Chuche, J. Eur. J. Org. Chem. 2000, 1019. (6) Rammah, M. M.; Othman, M.; Ciamala, K.; Strohmann, C.; Rammah, M. B. Tetrahedron 2008, 64, 3505. (7) (a) Del Buttero, P.; Molteni, G.; Pilati, T. Tetrahedron: Asymmetry 2010, 21, 2607. In this same context, see also:
Synlett 2011, No. 20, 30533054 Thieme Stuttgart New York

(8) (9)

(10) (11) (12)

(13)

(b) Lee, K. J.; Choi, J.-K.; Yum, E. K.; Cho, S. Y. Tetrahedron Lett. 2009, 50, 6698. Chen, K.; Baran, P. Nature 2009, 459, 824. This can be seen as a particular case of a more general concept coined as asymmetric counteranion-directed catalysis. For a leading reference, see: Mayer, S.; List, B. Angew. Chem. Int. Ed. 2006, 45, 4193. Hamilton, G.; Kanai, T.; Toste, F. D. J. Am. Chem. Soc. 2008, 130, 14984. (a) Wang, C.; Piel, I.; Glorius, F. J. Am. Chem. Soc. 2009, 131, 4194. For an intermolecular version, see: (b) Zhang, F.; Greaney, M. F. Org. Lett. 2010, 12, 4745. For a leading reference in this area see: Murai, S.; Kakiuchi, S.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda, M.; Chatani, N. Nature 1993, 366, 529. Wang, F.; Song, G.; Li, X. Org. Lett. 2010, 12, 5430.

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