Abstract
A facile and highly efficient copper- and palladium-free procedure
for the one-pot synthesis of ynones via coupling of sodium carboxylate
salts with alkynes is described. In this method, cross-coupling
of terminal alkynes with a mixture of structurally diverse sodium
carboxylate salts, cyanuric chloride and triethylamine in the presence
of magnesium chloride furnishes the corresponding ynones in good
to excellent yields at room temperature.
Key words
one-pot synthesis - alkyne - cyanuric chloride - sodium carboxylate salt - ynone
References and Notes
1a Mead D.
Asato AE.
Denny M.
Liu RSH.
Hanzawa Y.
Taguchi T.
Yamada A.
Kobayashi N.
Hosoda A.
Kobayashi Y.
Tetrahedron
Lett.
1987,
28:
259
1b Chowdhury C.
Kundu NG.
Tetrahedron
1999,
55:
7011
1c Quesnelle CA.
Gill P.
Dodier M.
St. Laurent D.
Serrano-Wu M.
Marinier A.
Martel A.
Mazzucco
CE.
Stickle TM.
Barrett JF.
Vyas DM.
Balasubramanian BN.
Bioorg. Med. Chem. Lett.
2003,
13:
519
2a Hojo M.
Omita K.
Hosomi A.
Tetrahedron Lett.
1993,
34:
485
2b Arcadi A.
Marenelli F.
Rossi E.
Tetrahedron
1999,
55:
13233
2c Kelin AV.
Sromek AW.
Gevorgyan V.
J. Am. Chem. Soc.
2001,
123:
2074
2d Jeevnandan A.
Narkunan K.
Ling Y.
J.
Org. Chem.
2001,
66:
6014
2e Grotjahn DB.
Van S.
Combs D.
Lev DA.
Schneider C.
Rideout M.
Meyer C.
Hernandez G.
Mejorado L.
J.
Org. Chem.
2002,
67:
9200
2f Karpov AS.
Muller TJ.
Org.
Lett.
2003,
5:
3451
3a Muzart J.
Piva O.
Tetrahedron
Lett.
1988,
29:
2321
3b Shaw JE.
Sherry JJ.
Tetrahedron
Lett.
1971,
4379
3c Sheats WB.
Olli LK.
Stout R.
Lundeen JT.
Justus R.
Nigh WG.
J.
Org. Chem.
1979,
44:
4075
4a Maeda Y.
Kakiuchi N.
Matsumura S.
Nishimura T.
Kawamura T.
Uemura S.
J.
Org. Chem.
2002,
67:
6718 ; and
references therein
4b Augé J.
Lubin-Germain N.
Seghrouchni L.
Tetrahedron
Lett.
2003,
44:
819
5a Corey EJ.
Kyler K.
Raju N.
Tetrahedron Lett.
1984,
25:
5115
5b Campestrini S.
Furia FD.
Modena G.
J.
Org. Chem.
1990,
55:
3658
5c Hirao T.
Misu D.
Agawa T.
Tetrahedron
Lett.
1986,
27:
933
6a Mohamed Ahmed MS.
Mori A.
Org. Lett.
2003,
5:
3057 ; and all references therein
6b Liang B.
Huang M.
You Z.
Xiong Z.
Lu K.
Fathi R.
Chen J.
Yang Z.
7a Goure WF.
Wright ME.
Davis PD.
Labadie SS.
Stille JK.
J.
Am. Chem. Soc.
1984,
106:
6417
7b Grisp GT.
Scott WJ.
Stille JK.
J. Am. Chem. Soc.
1984,
106:
7500
7c Arcadi A.
Cacchi S.
Marinelli F.
Ace P.
Sanzi G.
Synlett
1995,
823
8a Palimkar SS.
Harish Kumar P.
Jogdand NR.
Daniel T.
Lahoti RJ.
Srinivasan KV.
Tetrahedron Lett.
2006,
47:
5527
8b Alonso DA.
Nájera C.
Pacheco
MC.
J. Org. Chem.
2004,
69:
1615
8c Chen L.
Li C.-J.
Org. Lett.
2004,
6:
3151
8d Cox RJ.
Ritson DJ.
Dane TA.
Berge J.
Charmant JPH.
Kantacha A.
Chem. Commun.
2005,
1037
8e Likhar PR.
Subhas MS.
Roy M.
Roy S.
Kantam ML.
Helv. Chim. Acta
2008,
91:
259
8f Chen J.-Y.
Lin T.-C.
Chen S.-C.
Chen A.-J.
Mou C.-Y.
Tsai F.-Y.
Tetrahedron
2009,
65:
10134
8g Bakherad M.
Keivanloo A.
Bahramian B.
Rajaie M.
Tetrahedron Lett.
2010,
51:
33
9a Tohda Y.
Sonogashira K.
Hagihara N.
Synthesis
1977,
777
9b Verkruijsse HD.
Heus-Kloos YA.
Brandsma L.
J. Organomet. Chem.
1988,
338:
289
9c Logue MW.
Teng K.
J. Org. Chem.
1982,
47:
2549
9d Wakamatsu T.
Okuda Y.
Oshima K.
Nozaki H.
Bull. Chem. Soc. Jpn.
1985,
58:
2425
9e Pérez I.
Sestelo JP.
Sarandeses LA.
J. Am. Chem. Soc.
2001,
123:
4155
9f Kakusawa N.
Yamaguchi K.
Kurita J.
Tsuchiya T.
Tetrahedron Lett.
2000,
41:
4143
10 Davis RB.
Scheiber DH.
J. Am. Chem. Soc.
1956,
78:
1675
11a Normant JF.
Synthesis
1972,
63
11b Logue MW.
Moore GL.
J.
Org. Chem.
1975,
40:
131
12 Fontaine M.
Chauvelier J.
Barchewitz P.
Bull.
Soc. Chim. Fr.
1962,
2145
13 Compagnon PL.
Grosjean B.
Lacour M.
Bull.
Soc. Chim. Fr.
1975,
779
14 Yashina OG.
Zarva TV.
Vereshchagin LI.
Zh. Org. Khim.
1967,
3:
219 ; Chem. Abstr. 1967 , 66 , 94664
15 Vereshchagin LI.
Yashina OG.
Zarva TV.
Zh. Org. Khim.
1966,
2:
1895 ; Chem. Abstr . 1967 , 66 , 46070p
16a Utimoto K.
Tanaka M.
Kitai M.
Nozaki H.
Tetrahedron
Lett.
1978,
2301
16b Birkofer L.
Ritter A.
Uhlenbrauck H.
Chem.
Ber.
1963,
96:
3280
16c Walton
DRM.
Waugh F.
J.
Organomet. Chem.
1972,
37:
45
16d Gallagher WP.
Maleczka RE.
J.
Org. Chem.
2003,
68:
6775
17 Markó IE.
Southern JM.
J.
Org. Chem.
1990,
55:
3368
18 Himbert G.
Angew.
Chem., Int. Ed. Engl.
1979,
18:
405
19 Chowdhury C.
Kundu NG.
Tetrahedron Lett.
1996,
37:
7323
20a Lee KY.
Lee MJ.
Kim JN.
Tetrahedron
2005,
61:
8705
20b Keivanloo A.
Bakherad M.
Bahramian B.
Baratnia S.
Tetrahedron Lett.
2011,
52:
1498
21 Dishart KT.
Levine R.
J. Am. Chem. Soc.
1956,
78:
2268
22 Blotny G.
Tetrahedron
2006,
62:
9507 ; and all references cited therein
23a Soltani Rad MN.
Khalafi-Nezhad A.
Asrari Z.
Behrouz S.
Amini Z.
Behrouz M.
Synthesis
2009,
3983
23b Soltani Rad MN.
Khalafi-Nezhad A.
Asrari Z.
Behrouz S.
Synthesis
2010,
2599
24 Similar reaction conditions were employed
for carboxylic acid, except that Et3 N (6.6 equiv) was
employed
25a Venkataraman K.
Wagle DR.
Tetrahedron
Lett.
1979,
3037
25b Bandgar BP.
Pandit SS.
Tetrahedron
Lett.
2002,
43:
3413
25c Kaminski ZJ.
Paneth P.
Rudzinski J.
J. Org. Chem.
1998,
63:
4248
25d Rayle HL.
Fellmeth L.
Org. Process
Res. Dev.
1999,
3:
172
26 General procedure for coupling of
alkynes with sodium carboxylate salts using cyanuric chloride: To
a solution of sodium carboxylate salt (3.3 mmol) in anhydrous MeCN
(5 mL), was added TCT (1 mmol) and the reaction mixture was stirred
at r.t. for 10 min. A solution of the appropriate alkyne (3 mmol),
Et3 N (3.3 mmol) and MgCl2 (3.3 mmol) in anhydrous
MeCN (5 mL) was added and the solution was stirred for a further
50-110 min (until TLC indicated completion of the reaction,
see Table
[5 3 (50 mL) and subsequently
washed with H2 O (2 × 50 mL).
The organic layer was dried (Na2 SO4 ) and evaporated.
The crude product was purified by short column chromatography on
silica gel (n -hexane-EtOAc,
20:1).
