Direct and Selective Synthesis of Adipic and Other Dicarboxylic Acids by Palladium‐Catalyzed Carbonylation of Allylic Alcohols

Abstract

A general and direct synthesis of dicarboxylic acids including industrially important adipic acid by palladiumcatalyzed dicarbonylation of allylic alcohol is reported. Specifically, the combination of PdCl 2 and a bisphosphine ligand (HeMaRaphos) promotes two different carbonylation reactions with high activity and excellent selectivity.

Regioselective Coupling of Different Conjugate Esters by Magnesium Metal Reduction: A Route to Unsymmetrical Adipic Acid Esters

“…58% (385 mg), colorless oil, R f = 0.20, hexane:AcOEt = 10:1. 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.48 (d,J = 7.6 Hz,1H),2H),7.38 (d,J = 7.6 Hz,1H), 4.01 (d,J = 7.1 Hz,2H),3.60 (s,3H),1H),2.67 (dd,J = 15.6 Hz,7.1 Hz,1H),2.59 (dd,J = 15.6 Hz,7.1 Hz,1H),3H),1H), 1.11 (t, J = 7.1 Hz, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ (ppm): 173.…”

“…75% (417 mg), yellow oil, R f = 0.20, hexane:AcOEt = 10:1. 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.18 (t, J = 7.3 Hz, 1H), 7.02 (d, J = 7.3 Hz, 1H), 6.97 (s, 1H), 6.97 (d,J = 7.3 Hz,1H), 4.04 (q, J = 7.1 Hz, 1H), 3.61 (s, 3H), 3.10−3.02 (m, 1H), 2.63 (dd, J = 15.2 Hz, 7.1 Hz, 1H), 2.58 (dd, J = 15.2 Hz, 7.1 Hz, 1H), 2.32 (s, 3H), 2.25−1.99 (m, 3H), 1.93−1.83 (m, 1H), 1.15 (t, J = 7.1 Hz, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ (ppm): 173.…”

“…R f = 0.17, hexane:AcOEt = 10:1. 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.08 (d,J = 8.1 Hz,2H),7.04 (d,J = 8.1 Hz,2H), 4.02 (q, J = 7.1 Hz, 2H), 3.58 (s, 3H), 3.09−3.02 (m, 1H), 2.61 (dd, J = 15. 2 Hz,7.1 Hz,1H),2.56 (dd,J = 15.2 Hz,7.1 Hz,1H),2.29 (s,3H),2H),1H),1H), 1.13 (t, J = 7.1 Hz, 3H).…”

“…R f = 0.20, hexane:AcOEt = 10:1. 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.35 (d,J = 7.8 Hz,1H),2H),12 (m, 1H), 4.04 (q, J = 7.4 Hz, 2H), 3.80−3.75 (m, 1H), 3.61 (s, 3H), 2.64 (d, J = 7.4 Hz, 2H), 2.32−2.21 (m, 1H), 2.18−2.04 (m, 2H), 2.00−1.91 (m, 1H), 1.14 (t, J = 7.4 Hz, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ (ppm): 173.5, 171.5, 140.1, 134.4, 129.8, 127.8, 127.7, 127.1, 60.4, 51.5, 40.4, 37.0, 31.6, 30.4, 14.0 4H), 1.16 (t, J = 7.2 Hz, 3H).…”

“…R f = 0.20, hexane:AcOEt = 10:1. 1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 7.27 (d,J = 8.4 Hz,2H),7.11 (d,J = 8.4 Hz, 2H), 4.03 (q, J = 7.1 Hz, 2H), 3.61 (s, 3H), 3.13−3.06 (m, 1H), 2.62 (dd, J = 15.2 Hz, 7.1 Hz, 1H), 2.53 (dd, J = 15.2 Hz, 7.1 Hz, 1H), 2.21− 2.12 (m, 2H), 2.09−1.99 (m, 1H), 1.91−1.81 (m, 1H), 1.14 (t, J = 7.1 Hz, 3H). 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ (ppm): 173.4, 171.6, 141.1, 132.5, 128.9, 128.7, 60.4, 51.6, 41.5, 41.0, 31.8, 31.0, 14.1.…”