The kinetic resolution of 3‐aminopyrrolidine (3AP) and 3‐aminopiperidine (3APi) with ω‐transaminases was facilitated by the application of a protecting group concept. 1‐N‐Cbz‐protected 3‐aminopyrrolidine could be resolved with >99% ee at 50% conversion, the resolution of 1‐N‐Boc‐3‐aminopiperidine yielded 96% ee at 55% conversion. The reaction rate was up to 50‐fold higher by using protected substrates. Most importantly, enantioselectivity increased remarkably after carbamate protection compared to the unprotected substrates (86 vs. 99% ee). Surprisingly, benzyl protection of 3AP had no influence on enantioselectivity. A possible explanation for this observation could be the different flexibility of the benzyl‐ or carbamate‐protected 3AP as confirmed by NMR spectroscopy. 相似文献
A facile three‐step synthesis of racemic cyclopropylglycine in multigram quantities from inexpensive cyclopropyl methyl ketone has been elaborated. Enzymatic hydrolysis of the N‐Boc‐protected methyl ester of cyclopropylglycine 9 with the inexpensive enzyme papain from Carica papaya affords both enantiomers of cyclopropylglycine ( 8 ) with enantiomeric excesses of 99 % or better after deprotection under acidic conditions. Furthermore, the new cyclopropyl group‐containing building block methyl 2‐cyclopropyl‐2‐N‐Boc‐iminoacetate ( 13 ) was prepared by N‐chlorination and subsequent dehydrochlorination with 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU). Addition of nucleophiles to 13 offers a ready access to an unusual, orthogonally bisprotected α,α‐diamino acid derivative and interesting components of rigid peptide backbones. 相似文献
Polyaniline (PANI) has served as one of the most promising conducting materials in a variety of fields including sensors, actuators, and electrodes. Fabrication of 1D PANI fibers using electrospinning methods has gained a significant amount of attention. Due to the extremely poor solubility of PANI in common organic solvents, fabrication of electrospun PANI fiber has been carried out either by using corrosive solvents such as H2SO4 or by electrospinning in the presence of other matrix polymers. Herein, a new approach to the fabrication of PANI fibers using tert‐butyloxycarbonyl‐protected PANI (t‐Boc PANI) as the conducting polymer precursor is reported. The t‐Boc PANI is soluble in common organic solvents (e.g., chloroform and tetrahydrofuran), and electrospinning of t‐Boc PANI in those solvents affords nano/micrometer‐sized t‐Boc PANI fibers. Treatment of the electrospun t‐Boc PANI fibers with HCl results in the removal of the acid labile t‐Boc group and the generation of conducting (≈20 S cm?1) PANI fibers. The HCl‐doped PANI fibers are successfully used in the detection of gaseous ammonia with a detection limit of 10 ppm.