A Reductive Deuteration Approach to the Efficient Synthesis of Deuterated Polymers

Abstract

Deuterated polymers have wide applications but limited synthetic methods. In this study, we report an efficient two-step approach for the synthesis of deuterated polyesters and polyurethanes. Firstly, two practical single-electron transfer (SET) reductive-deuteration methods have been developed for site-selective introduction of C(sp³)–D into diol monomers. Nine deuterated diol monomers with high deuterium incorporations were synthesized under SmI₂–D₂O and/or Na-EtOD-d ₁ SET reductive-deuteration conditions. Then, six typical deuterated polyesters and polyurethanes were synthesized using those deuterated monomers under typical polymerization conditions. In all the synthesized polymers, high deuterium incorporation was fully maintained, which showcased the potential application of this approach for the synthesis of polymers with site-specific deuterium labelling.

Key words

reductive deuteration - single electron transfer - deuterated diol - deuterated polymer - selective deuteration

Publication History

Received: 25 January 2022

Accepted: 13 March 2022

Accepted Manuscript online:
13 March 2022

Article published online:
19 April 2022

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• 17a Typical Procedure for the Preparation of Model Compound 2a Using Na-EtOD-d ₁ To a solution of 1a (69.1 mg, 0.300 mmol, 1.00 equiv) in anhydrous hexane (2.50 mL) was added EtOD-d ₁ (3.60 mmol, 12.0 equiv) followed by Na dispersions in oil (34.5 wt%, 3.60 mmol, 12.0 equiv) under Ar at 0 ℃, and the resulting solution was stirred vigorously. After 20 min, the reaction was quenched by an aqueous solution of NaHCO₃ (5.0 mL, saturated), and the reaction mixture was diluted with EtOAc (10 mL) and brine (10 mL). The aqueous layer was extracted with EtOAc (3 × 15 mL), the organic layers were combined, dried over Na₂SO₄, filtered, and concentrated. The crude product was purified by flash chromatography (silica, 20–75% EtOAc/hexanes) to afford 2a (33.9 mg, 95%) as a white solid. Percentage of exchanged protons are determined by ¹H NMR spectroscopy indicated in square brackets. ¹H NMR (300 MHz, CDCl₃): δ = 1.61–1.42 (m, 6 H), 1.41–1.23 (m, 12 H). ¹³C{¹H}NMR (75 MHz, CDCl₃): δ = 62.4 (m), 32.7, 29.6, 29.5, 25.8.
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