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Partial synthesis of (3R,6'R)-alpha-cryptoxanthin and (3R)-beta-cryptoxanthin from (3R,3'R,6'R)-lutein.
J Nat Prod. 2007 Feb; 70(2):220-6.JN

Abstract

(3R,3'R,6'R)-Lutein (1), (3R,3'R)-zeaxanthin (2), (3R,6'R)-alpha-cryptoxanthin (3), and (3R)-beta-cryptoxanthin (4) are among dietary hydroxycarotenoids that have been identified in human serum, milk, and ocular tissues. While 1 containing 6% of 2 is commercially available, industrial production of optically active 3 and 4 has not yet been accomplished. Several processes have been developed that transform 1 into 3, 4, and minor quantities of (3R,5'RS,6'R)-3',4'-didehydro-5',6'-dihydro-beta,beta-caroten-3-ol (5) (a regioisomer of 3). In one process, lutein (1) was cleanly deoxygenated to 3 in the presence of trifluoroacetic acid (TFA) and Me3N.BH3 in CH2Cl2 at ambient temperature in nearly 90% yield. Reaction of lutein (1) with a Lewis acid (AlCl3, ZnBr2, ZnI2) and a hydride donor (Me3N.BH3, Na[BH3(OCOCF3)], NaCNBH3) in solvents such as CH2Cl2, THF, and TBME produced similar results. In a two-step process, high-temperature acid-catalyzed dehydration of 1 (propanol/water/acid, 90 degrees C) gave a mixture of anhydroluteins 6, 7, and 8 in 86% yield. In the second step, these dehydration products underwent ionic hydrogenation with TFA/Me3N.BH3 in CH2Cl2 to afford a mixture of 3 and 4 in nearly 80% yield that contained only 1% of 5.

Authors+Show Affiliations

Department of Chemistry and Biochemistry, Joint Institute for Food Safety and Applied Nutrition (JIFSAN), University of Maryland, College Park, Maryland 20742, USA. khachik@umd.eduNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

17266370

Citation

Khachik, Frederick, et al. "Partial Synthesis of (3R,6'R)-alpha-cryptoxanthin and (3R)-beta-cryptoxanthin From (3R,3'R,6'R)-lutein." Journal of Natural Products, vol. 70, no. 2, 2007, pp. 220-6.
Khachik F, Chang AN, Gana A, et al. Partial synthesis of (3R,6'R)-alpha-cryptoxanthin and (3R)-beta-cryptoxanthin from (3R,3'R,6'R)-lutein. J Nat Prod. 2007;70(2):220-6.
Khachik, F., Chang, A. N., Gana, A., & Mazzola, E. (2007). Partial synthesis of (3R,6'R)-alpha-cryptoxanthin and (3R)-beta-cryptoxanthin from (3R,3'R,6'R)-lutein. Journal of Natural Products, 70(2), 220-6.
Khachik F, et al. Partial Synthesis of (3R,6'R)-alpha-cryptoxanthin and (3R)-beta-cryptoxanthin From (3R,3'R,6'R)-lutein. J Nat Prod. 2007;70(2):220-6. PubMed PMID: 17266370.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Partial synthesis of (3R,6'R)-alpha-cryptoxanthin and (3R)-beta-cryptoxanthin from (3R,3'R,6'R)-lutein. AU - Khachik,Frederick, AU - Chang,An-Ni, AU - Gana,Audry, AU - Mazzola,Eugene, Y1 - 2007/02/01/ PY - 2007/2/3/pubmed PY - 2007/4/5/medline PY - 2007/2/3/entrez SP - 220 EP - 6 JF - Journal of natural products JO - J. Nat. Prod. VL - 70 IS - 2 N2 - (3R,3'R,6'R)-Lutein (1), (3R,3'R)-zeaxanthin (2), (3R,6'R)-alpha-cryptoxanthin (3), and (3R)-beta-cryptoxanthin (4) are among dietary hydroxycarotenoids that have been identified in human serum, milk, and ocular tissues. While 1 containing 6% of 2 is commercially available, industrial production of optically active 3 and 4 has not yet been accomplished. Several processes have been developed that transform 1 into 3, 4, and minor quantities of (3R,5'RS,6'R)-3',4'-didehydro-5',6'-dihydro-beta,beta-caroten-3-ol (5) (a regioisomer of 3). In one process, lutein (1) was cleanly deoxygenated to 3 in the presence of trifluoroacetic acid (TFA) and Me3N.BH3 in CH2Cl2 at ambient temperature in nearly 90% yield. Reaction of lutein (1) with a Lewis acid (AlCl3, ZnBr2, ZnI2) and a hydride donor (Me3N.BH3, Na[BH3(OCOCF3)], NaCNBH3) in solvents such as CH2Cl2, THF, and TBME produced similar results. In a two-step process, high-temperature acid-catalyzed dehydration of 1 (propanol/water/acid, 90 degrees C) gave a mixture of anhydroluteins 6, 7, and 8 in 86% yield. In the second step, these dehydration products underwent ionic hydrogenation with TFA/Me3N.BH3 in CH2Cl2 to afford a mixture of 3 and 4 in nearly 80% yield that contained only 1% of 5. SN - 0163-3864 UR - https://www.unboundmedicine.com/medline/citation/17266370/Partial_synthesis_of__3R6'R__alpha_cryptoxanthin_and__3R__beta_cryptoxanthin_from__3R3'R6'R__lutein_ L2 - https://dx.doi.org/10.1021/np060575v DB - PRIME DP - Unbound Medicine ER -