59277-20-2Relevant academic research and scientific papers
Convergent Synthesis of Menaquinone-7 (MK-7)
Baj, Aneta,Wa?ejko, Piotr,Kutner, Andrzej,Kaczmarek, ?ukasz,Morzycki, Jacek W.,Witkowski, Stanis?aw
, p. 1026 - 1033 (2016/11/11)
A practical synthesis of menaquinone-7 (MK-7, Vitamin K2) in the all-trans form was designed. Stereoselective synthesis of MK-7 was achieved through a "1 + 6" convergent strategy by condensation of two building blocks, menadione monoprenyl derivative (fragment "1") with hexaprenyl bromide (fragment "6", 82%). Pd-catalyzed desulfonation with LiEt3BH (78%) was followed by oxidation of the hydroquinone moiety using ammonium cerium(IV) nitrate (72%). The major challenge in our methodology was the preparation of all-trans hexaprenyl bromide by coupling of two triprenyl units derived from trans, trans-farnesol. Manufacturing on a pilot scale was accomplished through our approach. The scalable method was designed especially for a large, kilogram-scale production from easily available intermediates. Furthermore, the proposed methodology avoids many chromatographic purifications and allows for a relatively cost-effective manufacturing. Moreover, our synthesis yielded high-purity (99.9%) final product MK-7, which can be used as a dietary supplement as well as an active pharmaceutical ingredient.
Convergent synthesis of menaquinone-7 (MK-7)
Baj, Aneta,Wa?ejko, Piotr,Kutner, Andrzej,Kaczmarek, L?ukasz,Morzycki, Jacek W,Witkowski, Stanisl?aw
, p. 1026 - 1033 (2017/01/16)
A practical synthesis of menaquinone-7 (MK-7, vitamin K2) in the all-Trans form was designed. Stereoselective synthesis of MK-7 was achieved through a "1 + 6" convergent strategy by condensation of two building blocks, menadione monoprenyl derivative (fragment "1") with hexaprenyl bromide (fragment "6", 82%). Pd-catalyzed desulfonation with LiEt3BH (78%) was followed by oxidation of the hydroquinone moiety using ammonium cerium(IV) nitrate (72%). The major challenge in our methodology was the preparation of all-Trans hexaprenyl bromide by coupling of two triprenyl units derived from trans,trans-farnesol. Manufacturing on a pilot scale was accomplished through our approach. The scalable method was designed especially for a large, kilogram-scale production from easily available intermediates. Furthermore, the proposed methodology avoids many chromatographic purifications and allows for a relatively cost-effective manufacturing. Moreover, our synthesis yielded high-purity (99.9%) final product MK-7, which can be used as a dietary supplement as well as an active pharmaceutical ingredient.
LEWIS ACID INITIATED OR HIGH PRESSURE PROMOTED REACTIONS OF ISOPRENE WITH PHENYLSULFINYL CHLORIDE
Moiseenkov, A. M.,Veselovsky, V. V.,Makarova, Z. G.,Zhulin, V. M.,Smit, W. A.
, p. 5929 - 5932 (2007/10/02)
Lewis acid initiated reaction of isoprene with PhSOCl proceeds in a ene fashion with the formation of 2-phenylsulfinylmethyl-1,3-butadiene.High pressure promoted addition produces Z-1-phenylsulfinyl-4-chloroadduct presumably via cycloaddition.
ISOPRENE FUNCTIONALIZATION E/Z-ISOMERISM OF 1-SULFONYL SUBSTITUTED 2-METHYLBUTADIENES
Burger, J. J.,Chen, T. B. R. A.,Waard, E. R. De,Huisman, H. O.
, p. 723 - 726 (2007/10/02)
The isomeric chlorosulfones 3, 4 and 4 are prepared by 1,4-addition of sulfonyl chlorides to isoprene.Dehydrohalogenation affords the corresponding 2- and 3-methylbutadienyl sulfones in a configuration which is dependent on the configuration of the chlorosulfone.Pure Z-2-methylbutadienyl sulfones 1 are obtained by displacement of primary halides by the Z-sulfinate anion 2.The Z-sulfones 1 are isomerized to E/Z-mixtures.The E/Z-mixtures are separated into their components and the configuration of the isomers is established by the NMR-NOE technique.
