Abstract
Derivatives of 3,4-diaminopyridine have been synthesized and studied as catalysts for acyl-transfer reactions. The design of these catalysts is guided by the stability of their acetyl intermediates as determined through theoretical calculations at the B3LYP/6-311 + G(d,p)//B3LYP/6-31G(d) level of theory. The most promising catalysts have been synthesized through a three- to five-step synthesis starting from 3,4-diaminopyridine. The catalytic activity has been determined for the acylation of 1-ethynylcyclohexanol with acetic anhydride at 23 °C and with isobutyric anhydride at 40 °C. For both reactions, the catalytic activity depends dramatically on the substitution pattern of the diaminopyridines. Best results are obtained with catalysts containing alkyl substituents at both amine nitrogens.
Key words
catalysis - nucleophilic pyridines - acylation - alcohols
References
For reviews see:
1a
Höfle G.
Steglich W.
Vorbrüggen H.
Angew. Chem., Int. Ed. Engl.
1978,
17:
569 ; Angew. Chem. 1978, 90, 602
1b
Scriven EFV.
Chem. Soc. Rev.
1983,
12:
129
1c
Hassner A. In Encyclopedia of Reagents for Organic Synthesis
Paquette L.
Wiley;
Chichester:
1995.
p.2022
1d
Ragnarsson U.
Grehn L.
Acc. Chem. Res.
1998,
31:
494
1e
Spivey AC.
Maddaford A.
Redgrave A.
Org. Prep. Proced. Int.
2000,
32:
331
1f
Berry DJ.
Digiovanna CV.
Metrick SS.
Murugan R.
ARKIVOC
2001,
(i):
201 ; www.arkat-usa.org
1g
Spivey AC.
Arseniyadis S.
Angew. Chem. Int. Ed.
2004,
43:
5436 ; Angew. Chem. 2004, 116, 5552
2a
Vedejs E.
Jure M.
Angew. Chem. Int. Ed.
2005,
44:
3971 ; Angew. Chem. 2005, 117, 4040
2b
Dalko PI.
Moisan L.
Angew. Chem. Int. Ed.
2004,
43:
5138 ; Angew. Chem. 2004, 116, 5248
2c
Fu G.
Acc. Chem. Res.
2004,
37:
542
2d
France S.
Guerin DJ.
Miller SJ.
Lectka T.
Chem. Rev.
2003,
103:
2985
2e
Spivey AC.
Maddaford A.
Redgrave A.
Org. Prep. Proced. Int.
2000,
32:
331
2f
Fu G.
Acc. Chem. Res.
2000,
33:
412
3a
Kawabata T.
Stragies R.
Fukaya T.
Fuji K.
Chirality
2003,
15:
71
3b
Kawabata T.
Stragies R.
Fukaya T.
Nagaoka Y.
Schedel H.
Fuji K.
Tetrahedron Lett.
2003,
44:
1545
4a
Priem G.
Pelotier B.
Macdonald SJF.
Anson MS.
Campbell IB.
J. Org. Chem.
2003,
68:
3844
4b
Pelotier B.
Priem G.
Macdonald SJF.
Anson MS.
Upton RJ.
Campbell IB.
Tetrahedron Lett.
2005,
46:
9005
5a
Spivey AC.
Fekner T.
Spey SE.
Adams H.
J. Org. Chem.
1999,
64:
9430 ; and references cited therein
5b
Spivey AC.
Fekner T.
Spey SE.
J. Org. Chem.
2000,
65:
3154
5c
Spivey AC.
Maddaford A.
Fekner T.
Redgrave AJ.
Frampton CS.
J. Chem. Soc., Perkin Trans. 1
2000,
3460
5d
Spivey AC.
Maddaford A.
Fekner T.
Leese DP.
Redgrave AJ.
Frampton CS.
J. Chem. Soc., Perkin Trans. 1
2001,
1785
5e
Malardier-Jugroot C.
Spivey AC.
Whitehead MA.
J. Mol. Struct. (THEOCHEM)
2003,
623:
263
5f
Spivey AC.
Leese DP.
Zhu F.
Davey SG.
Jarvest RL.
Tetrahedron
2004,
60:
4513
5g
Spivey AC.
Arseniyadis S.
Fekner T.
Maddaford A.
Lees DP.
Tetrahedron
2006,
62:
295
6a
Dalaigh CO.
Hynes SJ.
Maher DJ.
Connon SJ.
Org. Biomol. Chem.
2005,
3:
981
6b
Dalaigh CO.
Hynes SJ.
O’Brien JE.
McCabe T.
Maher DJ.
Watson GW.
Connon SJ.
Org. Biomol. Chem.
2006,
4:
2785
7a
Shaw SA.
Aleman P.
Vedejs E.
J. Am. Chem. Soc.
2003,
125:
13368
7b
Shaw SA.
Aleman P.
Christy J.
Kampf JW.
Va P.
Vedejs E.
J. Am. Chem. Soc.
2006,
128:
925
8
Yamada S.
Misono T.
Iwai Y.
Tetrahedron Lett.
2005,
46:
2239
9a
Miller SJ.
Acc. Chem. Res.
2004,
37:
601 ; and references cited therein
9b
Fierman MB.
O’Leary DJ.
Steinmetz WE.
Miller SJ.
J. Am. Chem. Soc.
2004,
126:
6967
9c
Evans JW.
Fierman MB.
Miller SJ.
Ellman JA.
J. Am. Chem. Soc.
2004,
126:
8134
9d
Sculimbrene BR.
Xu Y.
Miller SJ.
J. Am. Chem. Soc.
2004,
126:
13182
9e
Morgan AJ.
Wang YK.
Roberts MF.
Miller SJ.
J. Am. Chem. Soc.
2004,
126:
15370
9f
Lewis CA.
Sculimbrene BR.
Xu Y.
Miller SJ.
Org. Lett.
2005,
7:
3021
9g
Xu Y.
Sculimbrene BR.
Miller SJ.
J. Org. Chem.
2006,
71:
4919
10
Singh S.
Das G.
Singh OV.
Han H.
Org. Lett.
2007,
9:
401
11
Heinrich MR.
Klisa HS.
Mayr H.
Steglich W.
Zipse H.
Angew. Chem. Int. Ed.
2003,
42:
4826 ; Angew. Chem. 2003, 115, 4975
12
Held I.
Villinger A.
Zipse H.
Synthesis
2005,
1425
13
Mederski WWKR.
Kux D.
Knoth M.
Schwarzkopf-Hofmann MJ.
Heterocycles
2003,
4:
925
14
Armand J.
Boulares L.
Bellec C.
Pinson J.
Can. J. Chem.
1988,
66:
1500
15
Moore ML.
Org. React.
1949,
5:
301
16
Sotirou-Leventis C.
Mao Z.
Rawashdeh A.-MM.
J. Org. Chem.
2000,
65:
6017
17a
Kison C.
Meyer N.
Opatz T.
Angew. Chem. Int. Ed.
2005,
44:
5662 ; Angew. Chem.
2005, 117, 5807
17b The large dependence of the reaction yield on the age of the BH3·THF solution described in this publication could be verified for the reduction of 24.
18
Sakamoto T.
Miura N.
Kondo Y.
Yamanaka H.
Chem. Pharm. Bull.
1986,
34:
2018
19
Claridge TDW.
High-Resolution NMR Techniques in Organic Chemistry, Tetrahedron Organic Chemistry Series
Vol. 19:
Pergamon;
Oxford:
1999.
p.298
20
Xu S.
Held I.
Kempf B.
Mayr H.
Steglich W.
Zipse H.
Chem. Eur. J.
2005,
11:
4751
21
Fischer CB.
Xu S.
Zipse H.
Chem. Eur. J.
2006,
12:
5779
22 The rate of reaction in these cases is hardly different from that of the uncatalyzed background reaction, making the exact determination of the half-lives rather difficult with the methodology employed here. The data given in Table
[2]
have been estimated from the conversion measured for reaction A up to 25 d, 17 h and 30 min and for reaction B up to 31 d, 17 h and 15 min. In both cases the reactions had not yet reached 50% conversion at these times.
23 The conversion of the reaction stopped at 59%. ESI-MS studies of the reaction mixture indicate that the catalyst does not survive the reaction conditions employed here.
24
Gottlieb HE.
Kotyar V.
Nudelman A.
J. Org. Chem.
1997,
21:
7512
25
Frisch MJ.
Trucks GW.
Schlegel HB.
Scuseria GE.
Robb MA.
Cheeseman JR.
Montgomery JA.
Vreven T.
Kudin KN.
Burant JC.
Millam JM.
Iyengar SS.
Tomasi J.
Barone V.
Mennucci B.
Cossi M.
Scalmani G.
Rega N.
Petersson GA.
Nakatsuji H.
Hada M.
Ehara M.
Toyota K.
Fukuda R.
Hasegawa J.
Ishida M.
Nakajima T.
Honda Y.
Kitao O.
Nakai H.
Klene M.
Li X.
Knox JE.
Hratchian HP.
Cross JB.
Bakken V.
Adamo C.
Jaramillo J.
Gomperts R.
Stratmann RE.
Yazyev O.
Austin AJ.
Cammi R.
Pomelli C.
Ochterski JW.
Ayala PY.
Morokuma K.
Voth GA.
Salvador P.
Dannenberg JJ.
Zakrzewski VG.
Dapprich S.
Daniels AD.
Strain MC.
Farkas O.
Malick DK.
Rabuck AD.
Raghavachari K.
Foresman JB.
Ortiz JV.
Cui Q.
Baboul AG.
Clifford S.
Cioslowski J.
Stefanov BB.
Liu G.
Liashenko A.
Piskorz P.
Komaromi I.
Martin RL.
Fox DJ.
Keith T.
Al-Laham MA.
Peng CY.
Nanayakkara A.
Challacombe M.
Gill PMW.
Johnson B.
Chen W.
Wong MW.
Gonzalez C.
Pople JA.
Gaussian 03, Revision B.03
Gaussian, Inc.;
Wallingford CT:
2004.
