RSS-Feed abonnieren
DOI: 10.1055/s-2003-44362
Copper(II) Tetrafluoroborate-Catalyzed Acetylation of Phenols, Thiols, Alcohols, and Amines
Publikationsverlauf
Publikationsdatum:
09. Dezember 2003 (online)
Abstract
Copper(II) tetrafluoroborate efficiently catalyzes acetylation of structurally diverse phenols, alcohols, thiols, and amines with stoichiometric amounts of Ac2O under solvent-free conditions at room temperature. Acid-sensitive alcohols are smoothly acetylated without competitive side reactions. The reaction is influenced by the steric and electronic factors associated with the substrate as well as the anhydride. Acetylation of a sterically hindered substrate requires excess of anhydride and longer time. Acylation with less electrophilic anhydrides affords poor to moderate yields.
Key words
acetylation - copper(II) tetrafluoroborate - solvent-free
-
1a
Greene TW.Wuts PGM. Protective Groups in Organic Synthesis 3rd ed.: Wiley; New York: 1999. -
1b
Hanson JR. Protective Groups in Organic Synthesis Blackwell Science Inc; Malden MA: 1999. -
2a
Chakraborti AK.Nayak MK.Sharma L. J. Org. Chem. 2002, 67: 1776 -
2b
Chakraborti AK.Nayak MK.Sharma L. J. Org. Chem. 2002, 67: 2541 -
2c
Chakraborti AK.Sharma L.Sharma U. Tetrahedron 2001, 57: 9343 -
2d
Chakraborti AK.Nayak MK.Sharma L. J. Org. Chem. 1999, 64: 8027 - 3
Steglich W.Höfle G. Angew. Chem., Int. Ed. Engl. 1969, 8: 981 -
4a
Iqbal J.Srivastava RR. J. Org. Chem. 1992, 57: 2001 -
4b
Ahmad S.Iqbal J. Tetrahedron Lett. 1986, 27: 3791 - 5
Vedejs E.Diver ST. J. Am. Chem. Soc. 1993, 115: 3358 -
6a
Ishihara K.Kubota M.Kurihara H.Yamamoto H. J. Am. Chem. Soc. 1995, 117: 4413 -
6b
Ishihara K.Kubota M.Kurihara H.Yamamoto H. J. Org. Chem. 1996, 61: 4560 - 7
Ishihara K.Kubota M.Yamamoto H. Synlett 1996, 265 -
8a
Procopiou PA.Baugh SPD.Flack SS.Inglis GGA. J. Org. Chem. 1998, 63: 2342 -
8b
Procopiou PA.Baugh SPD.Flack SS.Inglis GGA. Chem. Commun. 1996, 2625 - 9
Chauhan KK.Frost CG.Love I.Waite D. Synlett 1999, 1743 -
10a
Orita A.Tanahashi C.Kakuda A.Otera J. Angew. Chem., Int. Ed. 2000, 39: 2877 -
10b
Orita A.Tanahashi C.Kakuda A.Otera J. J. Org. Chem. 2001, 66: 8926 -
10c
Carrigan MD.Freiberg DA.Smith RC.Zerth HM.Mohan RS. Synthesis 2001, 2091 -
10d
Mohammadpoor-Baltork I.Aliyan H.Khosropour AR. Tetrahedron 2001, 57: 5851 -
11a
Saravanan P.Singh VK. Tetrahedron Lett. 1999, 40: 2611 -
11b
Chandra KL.Saravanan P.Singh RK.Singh VK. Tetrahedron 2002, 58: 1369 - 12
Chandrasekhar S.Ramachander T.Takhi M. Tetrahedron Lett. 1998, 39: 3263 - 13
Ballini R.Bosica G.Carloni S.Ciaralli L.Maggi R.Sartori G. Tetrahedron Lett. 1998, 39: 6049 -
14a
Bhaskar PM.Loganathan D. Tetrahedron Lett. 1998, 39: 2215 -
14b
Li A.-X.Li T.-S.Ding T.-H. Chem. Commun. 1997, 1389 - 15
Kumareswaran R.Pachamuthu K.Vankar YD. Synlett 2000, 1652 - 16
Kumar P.Pandey RK.Bodas MS.Dongare MK. Synlett 2001, 206 - 17
Nakae Y.Kusaki I.Sato T. Synlett 2001, 1584 - 18
Bartoli G.Bosco M.Dalpozzo R.Marcantoni E.Massaccesi M.Rinaldi S.Sambri L. Synlett 2003, 39 - 19
Dalpozzo R.De Nino A.Maiuolo L.Procopio A.Nardi M.Bartoli G.Romeo R. Tetrahedron Lett. 2003, 59: 5621 -
20a
Forsyth SA.MacFarlane DR.Thomson RJ.von Itzstein M. Chem. Commun. 2002, 714 -
20b
Lee S.-G.Park JH. J. Mol. Catal. A: Chem. 2003, 194: 49 - 21
Karimi B.Maleki J. J. Org. Chem. 2003, 68: 4951 - 22
Chakraborti AK.Gulhane R. Tetrahedron Lett. 2003, 44: 6749 -
23a
Sweet DV. Registry of Toxic Effects of Chemical Substances 1985-86 U. S. Govt. Printing Office; Washington D.C.: 1988. p.3336 -
23b
Sweet DV. Registry of Toxic Effects of Chemical Substances 1985-86 U. S. Govt. Printing Office; Washington D. C.: 1988. p.4049 - 24
Buckler SA. J. Am. Chem. Soc. 1962, 84: 3093 - 25
Olah GA.Prakash GKS. Superacids Wiley; New York: 1985. - 26
Chakraborti AK.Gulhane R. Tetrahedron Lett. 2003, 44: 3521 - 27
Chakraborti AK.Gulhane R. Chem. Commun. 2003, 1896 - 33
Garrett RL. In Designing Safer Chemicals American Chemical Society Symposium Series 640 Chap. 1:Garrett RL.De Vito SC. American Chemical Society; Washington D.C.: 1996.
References
Aldrich (India) 2003-2004 price (US $): Cu(BF4)2·xH2O (250 g, 107.80), In(OTf)3 (50 g, 417.00), Cu(OTf)2 (50 g, 416.00), Sc(OTf)3 (50 g, 1755.00), Sc(NTf2)3 (50 g, 3000.00), Ce(OTf)3 (? g, 421.50), LiOTf (100 g, 146.20). Estimated price (not being commercially available) (US $): Bi(OTf)3·xH2O (50 g, >315.95).
29Requirement of Ac2O(equiv): Sc(OTf)3 (1.5-as solvent), Sc(NTf2)3 (1.5), clays (2.0), zeolite (2.0), TMSOTf (1.5-as solvent), Cu(OTf)2 (2.0), Bi(OTf)3 (1.5-10), LiClO4 (2-10), Ce(OTf)3 (1.5), and LiOTf (5-8). Cu(BF4)2·xH2O(1).
30Requirement of high temperatures: Ytria-zirconia (80 °C), clays (40-80 °C), zeolite (60 °C), and LiClO4 (r.t.-40 °C). Low temperature required for acid-sensitive substrates: Cu(OTf)2 (-25 to 0 °C), Sc(OTf)3 (-50 to -20 °C), and TMSOTf (-10 °C). Cu(BF4)2·xH2O (r.t.).
31Requirement of longer times: Sc(OTf)3 (0.5-5 h), Sc(NTf2)3 (1 h), clays (2.5 h), zeolite (1.5-12 h), Cu(OTf)2 (1-2 h), Bi(OTf)3 (1-8.5 h), ytria-zirconia (2-15 h), LiClO4 (4-48 h), Ce(OTf)3 (0.2-24 h), and LiOTf (11-30 h). Cu(BF4)2·xH2O (0.25-1 h).
32Requirement of solvents: Sc(OTf)3 (MeCN or Ac2O); Sc(NTf2)3 (MeCN); clays (CH2Cl2 or CHCl3); ytria-zirconia (MeCN); TMSOTf (CH2Cl2, MeCN-EtOAc, Ac2O); Cu(OTf)2 (MeCN), Bi(OTf)3 (MeCN, THF, toluene, CH2Cl2), and Ce(OTf)3 (MeCN). Cu(BF4)2·xH2O (under neat conditions).