Transition metal-catalyzed protodecarboxylation of alpha-halo-acrylic acid derivatives
The present invention relates to a method for the synthesis of a halo olefin of formula (I) wherein Ha1, R 1 , R 2 , R 3 , R 4 , X and Y are as defined herein, or a salt thereof.
1. A compound selected from the group consisting of
wherein
R ar is selected from the group consisting of C(O)NR N1 R N2 and SO 2 NR N1 R N2 , wherein R N1 and R N2 are independently selected from the group consisting of H, substituted or unsubstituted C 1-6 -alkyl and substituted or unsubstituted C 3-7 -cycloalkyl; and
R Y1 and R Y2 are independently selected from the group consisting of H, substituted or unsubstituted acetyl, substituted or unsubstituted tert-butyloxycarbonyl (Boc), substituted or unsubstituted carboxybenzyl (Cbz), substituted or unsubstituted fluorenylmethyloxycarbonyl (Fmoc), substituted or unsubstituted allyloxycarbonyl (Alloc), substituted or unsubstituted tert-butyl, substituted or unsubstituted benzyl and substituted or unsubstituted phthaloyl, provided that at least one of R Y1 and R Y2 is not H, or
R Y1 and R Y2 are linked to form, together with N to which they are attached, substituted or unsubstituted phthalimide or substituted or unsubstituted pyrrole.
2. A compound selected from the group consisting of
wherein
R ar is selected from the group consisting of C(O)NR N1 R N2 and SO 2 NR N1 R N2 , wherein R N1 and R N2 are independently selected from the group consisting of H, substituted or unsubstituted C 1-6 -alkyl and substituted or unsubstituted C 3-7 -cycloalkyl; and
R Y1 and R Y2 are independently selected from the group consisting of H, substituted or unsubstituted acetyl, substituted or unsubstituted tert-butyloxycarbonyl (Boc), substituted or unsubstituted carboxybenzyl (Cbz), substituted or unsubstituted fluorenylmethyloxycarbonyl (Fmoc), substituted or unsubstituted allyloxycarbonyl (Alloc), substituted or unsubstituted tert-butyl, substituted or unsubstituted benzyl and substituted or unsubstituted phthaloyl or
R Y1 and R Y2 are linked to form, together with N to which they are attached, substituted or unsubstituted phthalimide or substituted or unsubstituted pyrrole.
3. A compound selected from the group consisting of
wherein
R ar is selected from the group consisting of C(O)NR N1 R N2 and SO 2 NR N1 R N2 , wherein R N1 and R N2 are independently selected from the group consisting of H, substituted or unsubstituted C 1-6 -alkyl and substituted or unsubstituted C 3-7 -cycloalkyl; and
R Y1 and R Y2 are independently selected from the group consisting of H, substituted or unsubstituted acetyl, substituted or unsubstituted tert-butyloxycarbonyl (Boc), substituted or unsubstituted carboxybenzyl (Cbz), substituted or unsubstituted fluorenylmethyloxycarbonyl (Fmoc), substituted or unsubstituted allyloxycarbonyl (Alloc), substituted or unsubstituted tert-butyl, substituted or unsubstituted benzyl and substituted or unsubstituted phthaloyl or
R Y1 and R Y2 are linked to form, together with N to which they are attached,
substituted or unsubstituted phthalimide or substituted or unsubstituted pyrrole; and
R 0 is selected from the group consisting of H and C 1-6 -alkyl.
4. A compound selected from the group consisting of
wherein
R ar is selected from the group consisting of C(O)NR N1 R N2 and SO 2 NR N1 R N2 , wherein R N1 and R N2 are independently selected from the group consisting of H, substituted or unsubstituted C 1-6 -alkyl and substituted or unsubstituted C 3-7 -cycloalkyl; and
R Y1 and R Y2 are independently selected from the group consisting of H, substituted or unsubstituted acetyl, substituted or unsubstituted tert-butyloxycarbonyl (Boc), substituted or unsubstituted carboxybenzyl (Cbz), substituted or unsubstituted fluorenylmethyloxycarbonyl (Fmoc), substituted or unsubstituted allyloxycarbonyl (Alloc), substituted or unsubstituted tert-butyl, substituted or unsubstituted benzyl and substituted or unsubstituted phthaloyl or
R Y1 and R Y2 are linked to form, together with N to which they are attached, substituted or unsubstituted phthalimide or substituted or unsubstituted pyrrole.
5. The compound of claim 1 which is compound (I-j).
6. The compound of claim 2 which is compound (II-j).
7. The compound of claim 2 which is compound (II-k).
8. The compound of claim 3 which is compound (II′-k).
9. The compound of claim 4 which is compound (III-j).