Functionalised cyclic dithiocarbamate synthesis method

1. A process for synthesizing a functionalized cyclic dithiocarbamate of formula (I):

in which

R 1 is a hydrogen or an aromatic or nonaromatic, linear or cyclic, saturated or unsaturated, branched or unbranched, hydrocarbon-based chain including from 1 to 20 carbon atoms, and which may, optionally, include one or more heteroatoms chosen from O, S, N, P and Si;

X represents —C(═O)— or —CH 2 — or —CN;

R 2 is (i) either nonexistent (when X represents —CN), (ii) or a hydrogen, (iii) or —OR 3 , R 3 being a hydrogen or an aromatic or nonaromatic, linear or cyclic, saturated or unsaturated, branched or unbranched, hydrocarbon-based chain including from 1 to 20 carbon atoms, and which may, optionally, comprise or more heteroatoms chosen from O, S, N, P and Si, (iv) or —NR 4 R 5 , with R 4 and R 5 , which are the same or different, being a hydrogen or an aromatic or nonaromatic, linear or cyclic, saturated or unsaturated, branched or unbranched, hydrocarbon-based chain including from 1 to 20 carbon atoms, and which may, optionally, include one or more heteroatoms chosen from O, S, N, P and Si;

n is equal to 0, 1 or 2; and

represents an asymmetric carbon;

said process comprising the steps of:

a/ providing at least one compound of formula (II):

G-(CH 2 ) n —C*H(NHR 1 )—X—R 2   (II)

in which

n, R 1 , R 2 , X and * are as defined previously,

G represents either (i) R 6 —C(═O)—O—CH 2 —, or (ii) (R 7 O)(R 8 O)—P(═O)—O—CH 2 —, or (iii) R 7 O—SO 2 —O—CH 2 —;

R 6 is a hydrogen or an aromatic or nonaromatic, linear or cyclic, saturated or unsaturated, branched or unbranched, hydrocarbon-based chain including from 1 to 20 carbon atoms, and which may, optionally, include one or more heteroatoms chosen from O, S, N, P and Si;

R 7 and R 8 , which may be identical or different, are chosen, independently of each other, from a proton H, an alkali metal, an alkaline-earth metal or an ammonium;

b/ providing at least one inorganic trithiocarbonate;

c/ reaction between said at least compound of formula (II) and said at least inorganic trithiocarbonate in the presence of at least one enzyme chosen from sulfhydrylases;

d/ production of at least one functionalized cyclic dithiocarbamate of formula (I);

e/ separation and isolation of said at least one functionalized cyclic dithiocarbamate of formula (I),

f/ optionally, additional functionalization of the functionalized cyclic dithiocarbamate of formula (I) obtained in step d/ or e/;

steps a/ and b/ optionally being performed simultaneously.

2. The process as claimed in claim 1 , in which the functionalized cyclic dithiocarbamate of formula (I) is enantiomerically pure.

3. The process as claimed in claim 1 , in which the functionalized cyclic dithiocarbamate of formula (I) is L-raphanusamic acid or L-homoraphanusamic acid.

4. The process as claimed in claim 1 , in which the compound of formula (II) is chosen from O-phospho-L-serine, O-succinyl-L-serine, O-acetyl-L-serine, O-acetoacetyl-L-serine, O-propio-L-serine, O-coumaroyl-L-serine, O-malonyl-L-serine, O-hydroxymethylglutaryl-L-serine, O-pimelyl-L-serine, O-sulfato-L-serine, O-succinyl-L-homoserine, O-acetyl-L-homoserine, O-acetoacetyl-L-homoserine, propio-L-homoserine, O-coumaroyl-L-homoserine, O-malonyl-L-homoserine, O-hydroxymethylglutaryl-L-homoserine, O-pimelyl-L-homoserine, O-phospho-L-homoserine and O-sulfato-L-homoserine.

5. The process as claimed in claim 1 , in which the sulfhydrylase is chosen from O-phospho-L-serine sulfhydrylase, O-succinyl-L-serine sulfhydrylase, O-acetyl-L-serine sulfhydrylase, O-acetoacetyl-L-serine sulfhydrylase, O-propio-L-serine sulfhydrylase, O-coumaroyl-L-serine sulfhydrylase, O-malonyl-L-serine sulfhydrylase, O-hydroxymethylglutaryl-L-serine sulfhydrylase, O-pimelyl-L-serine sulfhydrylase, O-sulfato-L-serine sulfhydrylase, O-phospho-L-homoserine sulfhydrylase, O-succinyl-L-homoserine sulfhydrylase, O-acetyl-L-homoserine sulfhydrylase, O-acetoacetyl-L-homoserine sulfhydrylase, O-propio-L-homoserine sulfhydrylase, O-coumaroyl-L-homoserine sulfhydrylase, O-malonyl-L-homoserine sulfhydrylase, O-hydroxymethylglutaryl-L-homoserine sulfhydrylase, O-pimelyl-L-homoserine sulfhydrylase and O-sulfato-L-homoserine sulfhydrylase.

6. The process as claimed in claim 1 , in which the inorganic trithiocarbonate is chosen from an alkali metal trithiocarbonate, an alkaline-earth metal trithiocarbonate and an ammonium trithiocarbonate.