Stereodivergent Synthesis of rac-cis- and rac-trans-4-Hydroxyphosphopipecolic Acids

Abstract

We report herein the first stereodivergent synthesis of rac-cis- and rac-trans-4-hydroxyphosphopipecolic acids. The main feature of this methodology is the controlled cis or trans reduction of 4-oxophosphopipecolates by exclusively varying the size of the hydride reagents. Thus, a small hydride reagent (NaBH₄) adds selectively from the axial side of the carbonyl group to give the equatorial hydroxyl group (cis-product), whereas a bulky hydride reagent such as LiBH(sec-Bu)₃ (L-Selectride^®) preferentially attacks from the equatorial side, giving the hydroxyl group in the axial position (trans-product). In the last step, hydrolysis of the diethyl phosphonate and ethyl phenylphosphinate groups with bromotrimethylsilane, followed by methanolysis, led to the target compounds.

Key words

stereodivergent synthesis - diastereoselective reduction - 4-hydroxyphosphopipecolic acid - heterocyclic α-aminophosphonic acids - heterocyclic α-aminophenylphosphinic acids

Publication History

Received: 11 October 2023

Accepted: 15 November 2023

Accepted Manuscript online:
15 November 2023

Article published online:
02 January 2024

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