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. Author manuscript; available in PMC: 2020 Jul 16.
Published in final edited form as: Dalton Trans. 2019 Jul 16;48(28):10581–10595. doi: 10.1039/c9dt02189b

Table 1.

Transition metal-catalyzed Z-isomerization of all-trans-retinoid using traditional heat treatment.a,b

graphic file with name nihms-1551403-t0010.jpg
Entry Sub Solvent Time Conversionc (%) Selectivity of 9-cisd (%) Product (3:2) Ratio range Effective Cat
1 1a C6H14 20 h 33-39 37-44 13-cis: 9-cis 1.2- 1.6: 1 I-V, VII
2 1b C6H14 20 h 15-34 21-98 13-cis: 9-cis 0- 3.9: 1 I, III-V, VII
3 1c C6H14 20 h 18-24 85-90 13-cis: 9-cis 0.1- 5.6: 1 I-V, VII
4 1d C6H14 20 h 16-21 77-94 13-cis: 9-cis 0.1- 0.6: 1 II, IV, VII
5 1e CH3CN 2 h 24 83 12-cis: 8-cis 0.2: 1 I
6 1f CH3CN 2 h 43-44 39-45 13-cis: 9-cis 0- 3: 1 I-V, XIX
7 1g CH3CN 2 h 33-46e 45-55 13-cis: 9-cis 0- 1.05: 1 I-XI
a

Reactions were carried out with all-trans-retinoid (0.1 mmol), catalyst (2 mol %), and TEA (0.2 μmol) at 65 °C under N2.

b

E/Z ratios reported are the average of two experiments and were determined by HPLC analysis.

c

Conversion to Z-isomer of the most effective catalysts.

d

Yields of 9-cis isomer for the most effective catalysts. 4.4 % of 9,13-dicis was detected. No reaction occurred without a catalyst for all substrates.