Huynh Mai T, Buchanan Emily, Chirayil Sara, Adebesin Adeniyi M, Kovacs Zoltan
Advanced Imaging Research Center, University of Texas Southwestern Medical Center, 5323 Harry Hines Blvd., Dallas, TX 75390, USA.
Department Biochemistry, University of Texas Southwestern Medical Center, 5323 Harry Hines Blvd., Dallas, TX 75390, USA.
Angew Chem Int Ed Engl. 2023 Nov 13;62(46):e202311669. doi: 10.1002/anie.202311669. Epub 2023 Sep 26.
Parahydrogen-induced polarization (PHIP) followed by polarization transfer to C is a rapidly developing technique for the generation of C-hyperpolarized substrates. Chirality plays an essential role in living systems and differential metabolism of enantiomeric pairs of metabolic substrates is well documented. Inspired by asymmetric hydrogenation, here we report stereoPHIP, which involves the addition of parahydrogen to a prochiral substrate with a chiral catalyst followed by polarization transfer to C spins. We demonstrate that parahydrogen could be rapidly added to the prochiral precursor to both enantiomers of lactic acid (D and L), with both the (R,R) and (S,S) enantiomers of a chiral rhodium(I) catalyst to afford highly C-hyperpolarized (over 20 %) L- and D-lactate ester derivatives, respectively, with excellent stereoselectivity. We also show that the hyperpolarized H signal decays obtained with the (R,R) and (S,S) catalysts were markedly different. StereoPHIP expands the scope of conventional PHIP to the production of C hyperpolarized chiral substrates with high stereoselectivity.
仲氢诱导极化（PHIP）随后将极化转移至碳是一种快速发展的用于生成碳超极化底物的技术。手性在生命系统中起着至关重要的作用，代谢底物对映体的差异代谢已有充分记录。受不对称氢化的启发，我们在此报告立体PHIP，它涉及用手性催化剂将仲氢添加到前手性底物上，随后将极化转移至碳自旋。我们证明，仲氢可以用手性铑（I）催化剂的（R,R）和（S,S）对映体快速添加到乳酸（D型和L型）两种对映体的前手性前体上，分别得到高度碳超极化（超过20%）的L - 和D - 乳酸酯衍生物，具有出色的立体选择性。我们还表明，用（R,R）和（S,S）催化剂获得的超极化氢信号衰减明显不同。立体PHIP将传统PHIP的范围扩展到具有高立体选择性的碳超极化手性底物的生产。
