Synthesis and use of deuterated palmitic acids to decipher the cryptoregiochemistry of a Δ13 desaturation

被引：5

作者：

Abad, Jose-Luis ^{[1
]}

Serra, Montserrat ^{[1
]}

Camps, Francisco ^{[1
]}

Fabrias, Gemma ^{[1
]}

机构：

[1] CSIC, Inst Invest Quim Ambientales Barcelona, Dept Quim Organ Biol, ES-08034 Barcelona, Spain

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 72卷 / 03期

关键词：

D O I：

10.1021/jo061592s

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The synthesis of two hexadeuterated palmitic acids differing in the position of the diagnostic labels, and their use to decipher the cryptoregiochemistry of a Delta(13) desaturation are described. A dithiane and a triple bond functionalities were used to introduce the diagnostic (C13 or C14) and tagging (C8 and C9) labels, respectively, in the palmitic acid skeleton. Using these probes, the cryptoregiochemistry of the Delta(13) desaturation involved in the biosynthesis of Thaumetopoea pityocampa sex pheromone was studied by means of kinetic isotope effect determinations. Transformation of both (Z)-11-hexadecenoic and 11-hexadecynoic acids into (Z, Z)-11,13-hexadecadienoic and (Z)-13-hexadecen-11-ynoic acids, respectively, is initiated by abstraction of the hydrogen atom at the C13 position, followed by the fast elimination of the C14 hydrogen to give the double bond.

引用

页码：760 / 764

页数：5

共 12 条

[1] Synthesis and use of stereospecifically deuterated analogues of palmitic acid to investigate the stereochemical course of the δ11 desaturase of the processionary moth [J].

Abad, JL ;

Villorbina, G ;

Fabriàs, G ;

Camps, F .

JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (21) :7108-7113

[2] Synthesis of deuterated fatty acids to investigate the biosynthetic pathway of disparlure, the sex pheromone of the gypsy moth, Lymantria dispar [J].

Abad, JL ;

Fabriàs, G ;

Camps, F .

LIPIDS, 2004, 39 (04) :397-401

[3] Synthesis of dideuterated and enantiomers of monodeuterated tridecanoic acids at C-9 and C-10 positions [J].

Abad, JL ;

Fabriás, G ;

Camps, F .

JOURNAL OF ORGANIC CHEMISTRY, 2000, 65 (25) :8582-8588

[4] Synthesis and use of probes to investigate the cryptoregiochemistry of the first animal acetylenase [J].

Abad, Jose-Luis ;

Rodriguez, Sergio ;

Camps, Francisco ;

Fabrias, Gemma .

JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (20) :7558-7564

[5] SYNTHESIS OF [16,16,16-H-2(3)] 11-HEXADECYNOIC ACID AND [15,15,16,16,16-H-2(5)] (Z,Z)-11,13-HEXADECADIENOIC ACID AND THEIR USE AS TRACERS IN A KEY STEP OF THE SEX-PHEROMONE BIOSYNTHESIS OF THE PROCESSIONARY MOTH [J].

BARROT, M ;

FABRIAS, G ;

CAMPS, F .

TETRAHEDRON, 1994, 50 (32) :9789-9796

[6] Mechanism of fatty acid desaturation in the green alga Chlorella vulgaris [J].

Behrouzian, B ;

Fauconnot, L ;

Daligault, F ;

Nugier-Chauvin, C ;

Patin, H ;

Buist, PH .

EUROPEAN JOURNAL OF BIOCHEMISTRY, 2001, 268 (12) :3545-3549

[7]

Frerot Brigitte, 1993, Bollettino di Zoologia Agraria e di Bachicoltura, V25, P33

[8] Identification of non-heme diiron proteins that catalyze triple bond and epoxy group formation [J].

Lee, M ;

Lenman, M ;

Banas, A ;

Bafor, M ;

Singh, S ;

Schweizer, M ;

Nilsson, R ;

Liljenberg, C ;

Dahlqvist, A ;

Gummeson, PO ;

Sjödahl, S ;

Green, A ;

Stymne, S .

SCIENCE, 1998, 280 (5365) :915-918

[9] Mechanism of 1,4-dehydrogenation catalyzed by a fatty acid (1,4)-desaturase of Calendula officinalis [J].

Reed, DW ;

Savile, CK ;

Qiu, X ;

Buist, PH ;

Covello, PS .

EUROPEAN JOURNAL OF BIOCHEMISTRY, 2002, 269 (20) :5024-5029

[10] GENERATION AND SYNTHETIC APPLICATIONS OF 2-LITHIO-1,3-DITHIANES [J].

SEEBACH, D ;

COREY, EJ .

JOURNAL OF ORGANIC CHEMISTRY, 1975, 40 (02) :231-237

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