One-pot Synthesis of 1,3-Butadiene and 1,6-Hexanediol Derivatives from Cyclopentadiene (CPD) via Tandem Olefin Metathesis Reactions

Turczel, Gábor and Kovács, Ervin and Csizmadia, Eszter and Nagy, Tibor and Tóth, Imre and Tuba, Robert (2018) One-pot Synthesis of 1,3-Butadiene and 1,6-Hexanediol Derivatives from Cyclopentadiene (CPD) via Tandem Olefin Metathesis Reactions. CHEMCATCHEM. ISSN 1867-3880

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Abstract

A novel tandem reaction of cyclopentadiene (CPD) leading to high value linear chemicals via ruthenium catalyzed ring opening cross metathesis (ROCM), followed by cross metathesis (CM) is reported. The ROCM of cyclopentadiene (CPD) with ethylene using commercially available 2nd gen. Grubbs metathesis catalysts (1‐G2) gives 1,3‐butadiene (BD) and 1,4‐pentadiene (2) (and 1,4‐cyclohexadiene (3)) with reasonable yields (up to 24 % (BD) and 67 % (2+3) at 73 % CPD conversion) at 1–5 mol % catalyst loading in toluene solution (5 V% CPD, 10 bar, RT) in an equilibrium reaction. The ROCM of CPD with cis‐butene diol diacetate (4) using 1.00 ‐ 0.05 mol % of 3rd gen. Grubbs (1‐G3) or 2nd gen. Hoveyda‐Grubbs (1‐HG2) catalysts loading gives hexa‐2,4‐diene‐1,6‐diyl diacetate (5), which is a precursor of 1,6‐hexanediol (an intermediate in polyurethane, polyester and polyol synthesis) and hepta‐2,5‐diene‐1,7‐diyl diacetate (6) in good yield (up to 68 % or TON: 1180). Thus, convenient and selective synthetic procedures are revealed by ROCM of CPD with ethylene and 4 leading to BD and 1,6‐hexanediol precursor, respectively, as key components of commercial intermediates of high‐performance materials.

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