Asymmetric synthesis of C-6 substituted pipecolic acid derivatives

Significance of the Natural Occurrence of L‐ Versus D‐Pipecolic Acid: A Review

“…L‐pipecolic acid is a precursor of many microbially derived biologically active compounds (Table ). Many studies have also described the synthetic preparation of pipecolic acid derivates including aryl‐ and alkyl‐substituted derivatives, cis ‐ and trans ‐5‐hydroxy‐D‐pipecolic acid from glycinate Schiff bases, C‐3‐, C‐4‐, C‐5‐, and C‐6‐substituted or paramagnetic DL‐pipecolic acid derivatives, or the enantioselective synthesis of 4,5‐dehydropipecolic acid (baikiain) …”

“…but not in Quercus or Castanea sp. Pipecolic acid betaine from the aerial parts of Lamium maculatum was isolated by Yuan et al 4‐Hydroxypipecolic acid (with antidiabetic and antioxidative properties) was found in the leaves and seeds of Caesalpinieae , and sulfate ester of trans ‐4‐hydroxypipecolic acid was detected in the seeds of Peltophorum africanum . cis ‐5‐Hydroxy‐L‐pipecolic acid was isolated from the leaves and seeds of Morus alba and y‐L‐glutamyl‐L‐pipecolic acid from the seeds of Gleditsia caspica .…”

“…Many studies have also described the synthetic preparation of pipecolic acid derivates including aryl-and alkyl-substituted derivatives, cis-and trans-5-hydroxy-D-pipecolic acid from glycinate Schiff bases, C-3-, C-4-, C-5-, and C-6-substituted or paramagnetic DL-pipecolic acid derivatives, or the enantioselective synthesis of 4,5-dehydropipecolic acid (baikiain). [42][43][44][45][46][47] 18 Umair and Simpson, 20 Chang and Adams, 21 Revelles et al, 22 Fujii et al, 23 Tsotsou and Barbirato, 24 Gatto et al, 25 Galili et al 79 ). Higher plants (A); Pseudomonas putida and P. putida KT 2440 (B); Escherichia coli transformed by the lat gene from Flavobacterium lutescens IFO3084 and proC gene from E. coli mutant RK4904 (C); microorganisms transformed by L-lysine cyclodeaminase (E. coli transformed by the SpLCD gene from Streptomyces pristinaespiralis and S. hygroscopicus NRRL 5491 disrupted by rapL gene) (D); animals (E).…”

“…46,119,120 Marlier et al 57 isolated 4,5-dihydroxy-L-pipecolic acid from Calliandra haematocephala, and C-4 oxygenated derivatives of pipecolic acid, including (2S, 4R)-4-hydroxypipecolic acid, were reported from the leaves of Calliandra pittieri and Strophanthus scandeus. 45 Marlier et al 58 isolated 2S-carboxy-4R,5S-dihydroxypiperidine and 2S-carboxy-4S, 5S-dihydroxypiperidine derived from pipecolic acid from the leaves of Derris elliptica; 2,4-trans-4,5-trans-4,5dihydroxypipecolic acid, cis-5-hydroxypipecolic acid (antifungal), 118 and trans-5-hydroxypipecolic acid (inhibitor of larvae growth) 117 were detected in the leaves of Calliandra angustifolia. 59 Uracilderived secondary metabolites of plants, including lathyrine metabolic modification, lead to the occurrence of cis-5-hydroxy-L-pipecolic acid.…”

“…4,5‐Dehydropipecolic acid (baikiain) with amnestic properties was found in Baikiaea plurijuga and other plants . Marlier et al isolated 4,5‐dihydroxy‐L‐pipecolic acid from Calliandra haematocephala , and C‐4 oxygenated derivatives of pipecolic acid, including (2 S , 4 R )‐4‐hydroxypipecolic acid, were reported from the leaves of Calliandra pittieri and Strophanthus scandeus . Marlier et al isolated 2 S ‐carboxy‐4 R ,5 S ‐dihydroxypiperidine and 2 S ‐carboxy‐4 S ,5 S ‐dihydroxypiperidine derived from pipecolic acid from the leaves of Derris elliptica ; 2,4‐ trans ‐4,5‐ trans ‐4,5‐dihydroxypipecolic acid, cis ‐5‐hydroxypipecolic acid (antifungal), and trans ‐5‐hydroxypipecolic acid (inhibitor of larvae growth) were detected in the leaves of Calliandra angustifolia .…”