Carbene Transfer Reactions Catalysed by Dyes of the Metalloporphyrin Group

Abstract

Carbene transfer reactions are very important transformations in organic synthesis, allowing the generation of structurally challenging products by catalysed cyclopropanation, cyclopropenation, carbene C-H, N-H, O-H, S-H, and Si-H insertion, and olefination of carbonyl compounds. In particular, chiral and achiral metalloporphyrins have been successfully explored as biomimetic catalysts for these carbene transfer reactions under both homogeneous and heterogeneous conditions. In this work the use of synthetic metalloporphyrins (MPorph, M = Fe, Ru, Os, Co, Rh, Ir, Sn) as homogeneous or heterogeneous catalysts for carbene transfer reactions in the last years is reviewed, almost exclusively focused on the literature since the year 2010, except when reference to older publications was deemed to be crucial.

Keywords: X-H insertion; carbenes; cyclopropanation; cyclopropenation; metalloporphyrins; olefination; porphyrins.

Scheme 1

The catalysed cyclopropanation reaction as an addition of a carbene group, from a diazo compound, to any alkene.

Scheme 2

The cyclopropanation of styrene (1) with methyl diazoacetate (MDA) or ethyl diazoacetate (EDA) (2, R = Me or Et) as a benchmark reaction.

Scheme 3

Intermolecular cyclopropanation of α-methylstyrene (5) by EDA catalysed by the Ru complexes of both the diamido and tetraamidoporphyrins [47].

Figure 1

The totem-like structure of the free base chiral porphyrin reported by Gallo and co-workers. Reproduced from [50] with permission from the Centre National de la Recherche Scientifique (CNRS) and The Royal Society of Chemistry.

Scheme 4

The chiral naphthyl-substituted tetraamidoporphyrin responsible for the higher enantioselectivity (99% ee) obtained in styrene (1) cyclopropanation with 2-methoxybenzaldehyde tosylhydrazone (6) at 83% yield and 95:5 trans/cis ratio. Adapted with permission from [51]. Copyright (2017) American Chemical Society.

Scheme 5

Asymmetric cyclopropanation of olefins with α-cyanodiazoacetates. Adapted with permission from [53]. Copyright (2010) American Chemical Society.

Scheme 6

Asymmetric cyclopropanation of olefins with α-ketodiazoacetates.

Scheme 7

The intermolecular cyclopropanation of styrene (1) with the N- and O-protected 6-diazo-5-oxo-l-norleucine (DON) (7) at ambient temperature in toluene and in the presence of metalloporphyrins.

Figure 2

Iron, ruthenium, and cobalt porphyrin complexes.

Figure 3

Cobalt porphyrin catalyst encapsulated in a cubic M₈L₆ cage. Adapted from [58] with permission from John Wiley and Sons.

Figure 4

The rhodium porphyrin was bound to the support by using the Williamson method for the synthesis of ethers, affording a loading around 1 mmol per gram of solid.

Scheme 8

Cyclopropanation reaction of 2-methoxystyrene (8) with EDA catalysed by DNA/iron(III) meso-tetrakis(N-methylpyridinium-yl)porphyrin hybrid catalysts.

Scheme 9

Cyclopropanation of 4-methoxystyrene (9) with EDA catalysed by Fe(TPP)Cl in aqueous media and in the presence or absence of E. coli.

Scheme 10

Cyclopropanation of styrene (1) with EDA catalysed by Ir(TTP)CH₃.

Scheme 11

Cyclopropanation of styrene derivative [1-chloro-4-(prop-1-en-2-yl)benzene] (10) with sodium 3-(N-methyl-N-nitrososulfamoyl)benzoate (11) as the diazomethane precursor catalysed by Fe(III) porphyrin dendrimers.

Scheme 12

Cyclopropanation of p-methoxystyrene (9) catalysed by Fe(TPP)Cl with sodium 3-(N-methyl-N-nitrososulfamoyl)benzoate (11) as the diazomethane precursor, under two-phase conditions.

Figure 5

The dendrimeric metalloporphyrin catalysts derived from the 5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin under conventional Williamson etherification conditions.

Scheme 13

Iron(III) porphyrin catalysed cyclopropanation reaction of styrenes in aqueous media.

Scheme 14

Fe(TPP)Cl catalysed cyclopropanation of 4-methoxystyrene (9) using (2,2,2-trifluoroethyl)diphenylsulfonium triflate (12) as the trifluoromethylcarbene precursor.

Scheme 15

Asymmetric cyclopropanation of styrene (1) with diazosulfones catalysed by Co(ZhuP2) [71].

Scheme 16

Asymmetric intramolecular cyclopropanation of allylic α-diazoacetates catalysed by Co(II) complexes of D₂-symmetric chiral amidoporphyrins.

Scheme 17

Co(II) porphyrin catalysed intramolecular cyclopropanation of (a) indolyl N-tosylhydrazones to form cyclopropane-fused indolines and (b) pyrrolyl N-arenesulfonylhydrazones to form cyclopropane-fused pyrrolines.

Scheme 18

Co(TTP) catalysed intramolecular Buchner reaction of (a) aniline derived N-tosylhydrazones and (b) arene cyclopropanation of naphthylamine derived N-tosylhydrazones.

Scheme 19

The intramolecular reaction catalysed by the Rh tetraarylporphyrin (with four phosphonate esters) that was covalently linked to the dielectric-electrolyte interface in the parallel plate cell.

Figure 6

The water-soluble Ru(II) glycosylated porphyrin complex used as catalyst for carbenoid transfer reactions in aqueous media [Ru^II(4-Glc-TPP)(CO)] (4-Glc-TPP = meso-tetrakis(4-(β-d-glucosyl)phenyl)porphyrinato dianion).

Scheme 20

Reactions catalysed by the water-soluble Ru(II) glycosylated porphyrin complex.

Scheme 21

Asymmetric cyclopropenation catalysed by a Co(II) chiral porphyrin.

Scheme 22

Intermolecular C-H insertion reactions of 1,4-cyclohexadiene with methyl phenyldiazoacetate catalysed by iridium(III) porphyrins.

Figure 7

Chiral iridium(III) porphyrins used for catalysed carbene C-H and Si-H bond insertion reactions.

Scheme 23

Intermolecular C-H insertion reactions of 1,4-cyclohexadiene with methyl aryldiazoacetate catalysed by the chiral porphyrin Ir(Halt)Me(L).

Scheme 24

Intermolecular C-H insertion reactions of THF (19) with methyl aryldiazoacetate (18) catalysed by the chiral porphyrin Ir(Halt)Me(L).

Scheme 25

Intermolecular C-H insertion reactions of cyclohexane (20) with EDA and MPDA catalysed by Ir(TTP)CH₃.

Scheme 26

Intramolecular C-H insertion of α-diazoester catalysed by the achiral porphyrin Ir(TTP)Me(L).

Scheme 27

Intramolecular C-H insertion of α-diazoester catalysed by the chiral porphyrin Ir(Halt)Me(L). The isolated yields are presented.

Figure 8

Octaethylporphyrin and tetraphenylporphyrin Ir(I) and Ir(III) complexes.

Scheme 28

Intramolecular C-H insertion catalysed by octaethylporphyrin and tetraphenylporphyrin Ir(I) and Ir(III) complexes.

Scheme 29

Rh(Porph)Me catalysed β-lactam and γ-lactam formation from α-diazoacetamides.

Scheme 30

Ru(II) porphyrin catalysed cyclization of N-tosylhydrazones to give tetrahydrofurans and pyrrolidines.

Scheme 31

Stereoselective C-H alkylation of a α-methoxycarbonyl-α-diazosulfone compound catalysed by a chiral Co(II)-Porph.

Figure 9

Examples of the 5-membered sulfolane derivatives resulting from the asymmetric C-H alkylation of α-methoxycarbonyl-α-diazosulfones, catalysed by a chiral Co(II) porphyrin developed by Zhang and co-workers [89].

Scheme 32

The intermolecular N-H insertion of aniline (25) with the N- and O-protected DON (7) at ambient temperature in toluene and in the presence of metalloporphyrins.

Scheme 33

The intramolecular N-H insertion with the unprotected DON (26) in water at ambient temperature and in the presence of a water-soluble ruthenium porphyrin.

Scheme 34

Carbene insertion into N-H bonds catalysed by iron(III) porphyrin microporous networks under heterogeneous conditions.

Scheme 35

Iron(III) porphyrin catalysed three-component reaction.

Scheme 36

Insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds catalysed by Fe(TPP)Cl.

Scheme 37

IrPMOF(Zr) synthesis by self-assembly of Ir(TCPP)Cl with ZrCl₄. Adapted from Ref. [100] with permission of The Royal Society of Chemistry.

Scheme 38

Reaction of EDA with aromatic and aliphatic thiols catalysed by Ir(TTP)CH₃ [101].

Scheme 39

Reaction of the protected DON (28) with thiols catalysed by Ru(TPP)(CO) or Fe(TPP)Cl.

Scheme 40

Synthesis of rotaxanes from α-diazoesters. Adapted from reference [103] with permission of Elsevier.

Scheme 41

Heterogeneous catalytic olefination of aldehydes catalysed by Fe(TPP)Cl microporous organic nanotube networks.