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. 2015 Jun 29:6:7508.
doi: 10.1038/ncomms8508.

Decarbonylative organoboron cross-coupling of esters by nickel catalysis

Kei Muto  1 , Junichiro Yamaguchi  1 , Djamaladdin G Musaev  2 , Kenichiro Itami  1   3
Affiliations

Decarbonylative organoboron cross-coupling of esters by nickel catalysis

Kei Muto et al. Nat Commun. .

Abstract

The Suzuki-Miyaura cross-coupling is a metal-catalysed reaction in which boron-based nucleophiles and halide-based electrophiles are reacted to form a single molecule. This is one of the most reliable tools in synthetic chemistry, and is extensively used in the synthesis of pharmaceuticals, agrochemicals and organic materials. Herein, we report a significant advance in the choice of electrophilic coupling partner in this reaction. With a user-friendly and inexpensive nickel catalyst, a range of phenyl esters of aromatic, heteroaromatic and aliphatic carboxylic acids react with boronic acids in a decarbonylative manner. Overall, phenyl ester moieties function as leaving groups. Theoretical calculations uncovered key mechanistic features of this unusual decarbonylative coupling. Since extraordinary numbers of ester-containing molecules are available both commercially and synthetically, this new 'ester' cross-coupling should find significant use in synthetic chemistry as an alternative to the standard halide-based Suzuki-Miyaura coupling.

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Figures

Figure 1
Figure 1. Esters as electrophiles in the Suzuki–Miyaura coupling.
(a) Electrophiles (R–Z) in the Suzuki–Miyaura coupling with organoboron compounds catalysed by palladium or nickel; Z=halogen (standard), Z=N, O, S (emerging), Z=CO2Ph (esters; this work). (b) Advantages of using esters as electrophilic coupling partners in Suzuki–Miyaura coupling. (c) Our mechanistic blueprint of decarbonylative cross-coupling of esters and boronic acids catalysed by nickel.
Figure 2
Figure 2. Calculation of nickel-catalysed reaction.
(a) Schematic presentation of the elementary steps of the decarbonylative coupling of phenyl 3-pyridinecarboxylate and p-anisylboronic acid in the presence of Ni-P(nBu)3 and Na2CO3. (b) The important reactive intermediates B and D, and transmetalation transition state TS2. Hydrogen atoms and n-butyl groups on phosphorous atoms are omitted for clarity. (c) Relative energies of representative intermediates and transition states. The presented Gibbs free relative energies (ΔG) are obtained at the M06/{Lanl2dzNi+[6–31G(d,p)]} level of theory, in toluene solution (by using the polarizable continuum model (PCM) solvation method), and at the experimentally reported temperature (423.15 K) and pressure (1 atm).
Figure 3
Figure 3. Further applications of ‘ester' Suzuki–Miyaura coupling.
(a) One-pot transformation of thiophene-2-carboxylic acid to biaryl 3Ka. (b) Application to the synthesis of telmisartan derivatives. (c) Orthogonal coupling of 6; decarbonylative cross-coupling catalysed by Ni(OAc)2/P(n-Bu)3 (first step) and C–H/C–O coupling catalysed by Ni(cod)2/dcypt (second step). dcypt, 3,4-bis(dicyclohexylphosphino)thiophene. (d) Sequential coupling of 1Q; decarbonylative C–B coupling catalysed by Ni(OAc)2/P(n-Bu)3 (first step) and decarbonylative C–H coupling catalysed by Ni(cod)2/dcype (second step). (e) Orthogonal coupling of 10: decarbonylative C–H coupling catalysed by Ni(cod)2/dcype (first step) and decarbonylative C–B coupling catalysed by Ni(OAc)2/P(n-Bu)3 (second step).
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References

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