3
corresponding anhydrides (6f, 6g and 6h, Scheme 3).13 To the
best of our knowledge, the synthesis of anhydrides from alcohols
by an oxidative self coupling is unprecedented. A plausible
47, 162-165; (b) Kocz, R.; Roestamadji, J.; Mobashery, S. J.
Org. Chem. 1994, 59, 2913-2914.
2. Kazemi, F.; Sharghi, H.; Nasseri, M. A. Synthesis 2004, 2, 205-
207.
3. (a) Fife, W. K.; Zhang, Z. D. Tetrahedron Lett. 1986, 27, 4937-
4940; (b) Kazemi, F.; Kiasat, A. R. Phosphorus, Sulfur Silicon
reaction mechanism is described on Scheme 4. On the basis of
14
formerly published papers12a,
alcohol A reacts with TCCA,
Relat. Elem. 2003, 178, 2287-2291; (c) Kazemi, F.; Kiasat, A. R.;
Mombaini, B. Synth. Commun. 2007, 37, 3219-3223.
4. (a) Mestres, R.; Palomo, C. Synthesis 1981, 3, 218-220; (b)
Kawamura, Y.; Sato, Y.; Horie, T.; Tsukayama, M. Tetrahedron
Lett. 1997, 38, 7893-7896.
5. Keshavamurthy, K. S.; Vankar , Y. D.; Dhar, D. N. Synthesis
1982, 6, 506-508
6. Kamiñski, Z. J.; Kolesiñska, B.; Małgorzata, M. Synth. Commun.,
2004, 34, 3349-3358.
7. (a) Hata, T.; Tajima, K.; Mukaiyama, T. Bull. Chem. Soc. Jpn.
1968, 41, 2746-2747; (b) Stadler, A; Kappe, C. O. Tetrahedron
2001, 57, 3915-3920; (c) Clarke, P. A.; Kayaleh, N. E.; Smith, M.
A.; Baker, J. R.; Bird, S. J.; Chan, C. J. Org. Chem. 2002, 67,
5226-5231.
generating the hypochlorite compound B, which loses hydrogen
chloride to form the aldehyde C. Then aldehyde C is converted
into the acyl chloride D, through a radical pathway.15, 16 Then, the
acyl chloride
D reacts with triethylamine to form the
acylammonium complex E,17 of which part reacts with water to
form the carboxylate F.14 Finally the acylammonium complex E
and the carboxylate F react leading to the formation of the
anhydride G.14
8. (a) Ekoue-Kovi, K.; Wolf, C. Chem. Eur. J. 2008, 14, 6302-6315;
(b) Tang, S.; Yuan, J.; Liu. C.; Lei, A. Dalton Trans. 2014, 43,
13460-13470
9. Khatun, N.; Santra, S. K.; Banerjee, A.; Patel, B. K. Eur. J. Org.
Chem. 2015, 1309-1313.
10. (a) Saberi, D.; Shojaeyan, F.; Niknam, K. Tetrahedron Lett. 2016,
57, 566-569; (b) Singha, R.; Ghosh, M.; Nuree, Y.; Ray, J. K.
Tetrahedron Lett. 2016, 57, 1325-1327; (c) Nuree, Y.; Singha, R.;
Ghosh, M.; Roy, P.; Ray, J. K. Tetrahedron Lett. 2016, 57, 1479-
1482; (d) Adib, M.; Pashazadeh, R.; Rajai-Daryasarei, S.; Mirzaei,
P.; Gohari, S. J. A. . Tetrahedron Lett. 2016, 57, 3071-3074.
11. Gaspa, S.; Amura, I.; Porcheddu, A.; De Luca, L. New J. Chem.
2017, 41, 931-939.
Scheme 4. Proposed reaction mechanism
12. (a) Gaspa, S.; Porcheddu, A.; De Luca, L. Adv. Synth. Catal. 2016,
358, 154-158; (b) Dettori, G.; Gaspa, S.; Porcheddu, A.; De Luca,
L. Org. Biomol. Chem. 2014, 12, 4582-4585; (c) Gaspa, S.;
Porcheddu, A.; De Luca, L. Org. Biomol. Chem. 2013, 11, 3803-
3807.
13. When aliphatic alcohols were employed, no corresponding
anhydrides were obtained, since aliphatic alcohols were not
oxidized to the corresponding aldehydes under the optimized
conditions.
14. Dhimitruka, I.; SantaLucia, J. Org. Lett. 2006, 8, 47-50.
15. Gaspa, S.; Porcheddu, A.; De Luca, L. Org. Lett. 2015, 17, 3666-
3669.
16. (a) Veisi, H. Synthesis 2010, 2631-2635; (b) Srilakshmi-
Krishnaveni, N.; Suredra, K.; Rama Rao, K. Adv. Synth. Catal.
2004, 346, 346-350; (c) Tilstam, U.; Weinmann, H. Org. Process
Res. Dev. 2002, 6, 384-393; (d) Filler, R. Chem. Rev. 1963, 63,
21-43.
2. Conclusion
In conclusion, we have developed an easy metal-free and
versatile oxidative self-coupling of aldehydes or primary alcohols
to their symmetrical anhydrides. A variety of both aromatic and
aliphatic aldehydes and primary benzylic alcohols were used in
this methodology and the corresponding anhydrides were
obtained in satisfactory yields. The methodology has an optimal
stoichiometric molar ratio of reactants, and makes use of green
reagents and mild reaction conditions.
Acknowledgments
17. Hubbard, P.; Brittain, W. J. J. Org. Chem. 1998, 63, 677-683.
This work was financially supported by Regione autonoma
della Sardegna within the project:”Valorizzazione di biomasse
d’interesse regionale attraverso processi chimici a basso impatto
ambientale”(CRP 72-Bando “Capitale Umano ad Alta
Qualificazione. Annualità 2015_L.R. 7 agosto 2007, n°7”). Silvia
Gaspa gratefully acknowledges Sardinia Regional Government
for the financial support of her PhD scholarship (P.O.R. Sardegna
F.S.E. Operational Programme of the Autonomous Region of
Sardinia, European Social Fund 2007– 2013-Axis IV Human
Resources, Objective l.3, Line of Activity l.3.1).
Supplementary Material
Supplementary material that may be helpful in the review
process should be prepared and provided as a separate electronic
file. That file can then be transformed into PDF format and
submitted along with the manuscript and graphic files to the
appropriate editorial office.
References and notes
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