Abstract
Diethanolamine-complexed heterocyclic boronic acids (DABO boronates)
are air-stable reagents that can be used directly in Suzuki-Miyaura
reactions in the presence of water or a protic co-solvent. Interestingly,
heterocyclic DABO boronates can be stored for extended periods of
time at room temperature with no noticeable degradation, unlike
their boronic acid counterparts. Heterocyclic DABO boronates constitute
an operationally simple and efficient alternative to other boronic
acid derivatives as coupling partners in palladium-catalyzed cross-coupling
reactions under standard Suzuki-Miyaura conditions.
Key words
Suzuki-Miyaura reaction - cross-coupling - palladium catalysis - heterocyclic boronate - aryl
boronate
References
1
Miyaura N.
Suzuki A.
Chem. Rev.
1995,
95:
2457
2
Nicolaou KC.
Bulger PG.
Sarlah D.
Angew.
Chem. Int. Ed.
2005,
44:
4442
3
Hayashi T.
Yamasaki K.
Chem. Rev.
2003,
103:
2829
4
Lin P.-S.
Jeganmohan M.
Cheng C.-H.
Chem.
Eur. J.
2008,
14:
11296
5
Hall DG.
Boronic Acids
Wiley-VCH;
Weinheim:
2005.
6
Billingsley K.
Buchwald SL.
J. Am. Chem. Soc.
2007,
129:
3358
7
Molander GA.
Canturk B.
Kennedy LE.
J.
Org. Chem.
2009,
74:
973
8
Molander GA.
Bernardi CR.
J. Org. Chem.
2002,
67:
8424
9
Molander GA.
Sandrock DL.
Curr. Opin. Drug Discovery
Dev.
2009,
12:
811
10
Mancilla T.
Contreras R.
Wrackmeyer B.
J.
Organomet. Chem.
1986,
307:
1
11
Gillis EP.
Burke MD.
J. Am. Chem. Soc.
2007,
129:
6716
12
Knapp DM.
Gillis EP.
Burke MD.
J. Am. Chem. Soc.
2009,
131:
6961
13
Alessi M.
Larkin AL.
Ogilvie KA.
Green LA.
Lai S.
Lopez S.
Snieckus V.
J. Org. Chem.
2007,
72:
1588
14
Bouillon A.
Lancelot J.-C.
Santos JS.
Callot V.
Bovy PR.
Rault S.
Tetrahedron
2003,
59:
10043
15
Hodgson PB.
Salingue FH.
Tetrahedron Lett.
2004,
45:
685
16
Gros P.
Doudouh A.
Fort Y.
Tetrahedron
Lett.
2004,
45:
6239
17
Davies AG.
Roberts BP.
Ramsay W.
J.
Chem. Soc. B
1967,
17
18
Letsinger RL.
Skoog I.
J. Am. Chem. Soc.
1955,
77:
2491
19 Crystallographic data: Rettig SJ.
Trotter J.
Can.
J. Chem.
1975,
53:
1393
20 MIDA is over 100 times more expensive.
KHF2 is similarly priced, but 3.0 equiv are required
for the synthesis of heterocyclic potassium trifluoroborates. Pinacol
is about 10 times more expensive than DEA. Prices were obtained
from the Sigma-Aldrich online catalogue.
21 2-Methoxyphenylboronic acid and 2-furyl
DABO boronate 7 were mixed at r.t. in THF
for 3 h to give an equilibrium mixture of both boronic acids and
their DABO counterparts. A similar product mixture was observed
beginning with 2-methoxyphenyl DABO boronate 4 and
2-furylboronic acid.
22
Caron S.
Hawkins JM.
J. Org. Chem.
1998,
63:
2054
23
Bonin H.
Leuma-Yona R.
Marchiori B.
Demonchaux P.
Gras E.
Tetrahedron
Lett.
2011,
52:
1132
24 Excess diethanolamine can be removed
by triturating the crude solid in EtOAc and filtering. DABO complexes
could not be characterized by HRMS, and unidentifiable boron-containing
masses were observed by electron ionization. Elemental analysis
was attempted, but the carbon percentage was consistently below
the theoretical value by about 10.
25 No decomposition of 2-furyl DABO boronate 7 was observed by NMR analysis after 72
d of storage in open vials at r.t. The average temperature and humidity
were 24 ˚C and 65%, respectively, during
this period. In contrast, the commercial 2-furylboronic acid completely
decomposed in less than one week under these conditions. We recommend storing
DABO boronates at r.t. in a closed vial.
26
Inoue M.
Frontier AJ.
Danishefsky SJ.
Angew. Chem. Int. Ed.
2000,
39:
761
27
Wang Z.
Elokdah H.
McFarlane G.
Pan S.
Antane M.
Tetrahedron
Lett.
2006,
47:
3365
28
Molander GA.
Yun C.-S.
Tetrahedron
2002,
58:
1465