Carbene complexes with rhodium porphyrins

Mechanistic studies of rhodium porphyrins as cyclopropanation catalysts have resulted in the spectroscopic identification of several potential intermediates in the reaction of ethyl diazoacetate with olefins, including a diazoniumfethoxy-carbonyl)methyl-rhodium complex formed by electrophilic addition of the rhodium center to the a-C atom of ethyl diazoacetate [29]. It is not known if analogous intermediates are also formed in analogous reactions of copper catalysts. However, the initial part of the catalytic cycle leading to the metal carbene intermediate is not of primary concern for the enantioselective reactions described herein. It is the second part, the reaction of the metal-carbene complex with the substrate, that is the enantioselective step. 

The Lewis acid-Lewis base interaction outlined in Scheme 43 also explains the formation of alkylrhodium complexes 414 from iodorhodium(III) meso-tetraphenyl-porphyrin 409 and various diazo compounds (Scheme 42)398), It seems reasonable to assume that intermediates 418 or 419 (corresponding to 415 and 417 in Scheme 43) are trapped by an added nucleophile in the reaction with ethyl diazoacetate, and that similar intermediates, by proton loss, give rise to vinylrhodium complexes from ethyl 2-diazopropionate or dimethyl diazosuccinate. As the rhodium porphyrin 409 is also an efficient catalyst for cyclopropanation of olefins with ethyl diazoacetate 87,1°°), stj bene formation from aryl diazomethanes 358 and carbene insertion into aliphatic C—H bonds 287, intermediates 418 or 419 are likely to be part of the mechanistic scheme of these reactions, too. 

The q1-coordinated carbene complexes 421 (R = Ph)411 and 422412) are rather stable thermally. As metal-free product of thermal decomposition [421 (R = Ph) 110 °C, 422 PPh3, 105 °C], one finds the formal carbene dimer, tetraphenylethylene, in both cases. Carbene transfer from 422 onto 1,1-diphenylethylene does not occur, however. Among all isolated carbene complexes, 422 may be considered the only connecting link between stoichiometric diazoalkane reactions and catalytic decomposition [except for the somewhat different results with rhodium(III) porphyrins, see above] 422 is obtained from diazodiphenylmethane and [Rh(CO)2Cl]2, which is also known to be an efficient catalyst for cyclopropanation and S-ylide formation with diazoesters 66). 

The preparation of cyclopropanes by intermolecular cyclopropanation with acceptor-substituted carbene complexes is one of the most important C-C-bond-forming reactions. Several reviews [995,1072-1074,1076,1077,1081] and monographs have appeared. In recent decades chemists have focused on stereoselective intermolecular cyclopropanations, and several useful catalyst have been developed for this purpose. Complexes which catalyze intermolecular cyclopropanations with high enantiose-lectivity include copper complexes [1025,1026,1028,1029,1031,1373,1398-1400], cobalt complexes [1033-1035], ruthenium porphyrin complexes [1041,1042,1230], C2-symmetric ruthenium complexes [948,1044,1045], and different types of rhodium complexes [955,998,999,1002-1004,1010,1062,1353,1401-1405], Particularly efficient catalysts for intermolecular cyclopropanation are C2-symmetric cop-per(I) complexes, as those shown in Figure 4.20. These complexes enable the formation of enantiomerically enriched cyclopropanes with enantiomeric excesses greater than 99%. Illustrative examples of intermolecular cyclopropanations are listed in Table 4.24. 

In addition to copper and rhodium catalysts commonly used in the generation of metal carbene complexes, other transition metals have also been explored in the diazo decomposition and subsequent ylide generation.Che and co-workers have recently studied ruthenium porphyrin-catalyzed diazo decomposition and demonstrated a three-component coupling reaction of a-diazo ester with a series of iV-benzylidene imines and alkenes to form functionalized pyrrolidines in excellent diastereoselectivities (Scheme 20). ... 

Reactions of rhodium porphyrins with diazo esters - According to Callot et al., iodorhodium(III) porphyrins are efficient catalysts for the cyclopropanation of alkenes by diazo esters [320,321], The transfer of ethoxycarbonylcarbene to a variety of olefins was found to proceed with a large syn-selectivity as compared with other catalysts. In their study to further develop this reaction to a shape-selective and asymmetric process [322], Kodadek et al. [323] have delineated the reaction sequences (29, 30) and identified as the active catalyst the iodoalkyl-rhodium(III) complex resulting from attack of a metal carbene moiety Rh(CHCOOEt) by iodide. 

Iodorhodium(IIl) porphyrins also efficiently catalyze the reaction of ethyl diazoacetate with simple alkenes. generally providing the cw-isomers as the major product77 79110. The cis( tram ratio increases when bulkier porphyrins, such as tetramesitylporphyrin (TMP), are employed. The mechanism of this rhodium-catalyzed cyclopropanation with diazoacetate is interpreted as proceeding via carbene complexes79 80 111,112. Based on these results, asymmetric cyclopropanation of alkenes with ethyl diazoacetate is achieved if catalyzed by a chiral wall porphyrin81. An earlier described binaphthyl-system of this type82113114, introduced as an iodorhodium(lll) complex, 6, forms an extremely active catalyst and leads to m-cyclopropanes (preferred over the rran.v-products) with moderate to poor enantioselectivities if styrene, 1- and 3-phenylpropene are used as substrates (10-60% ee)81. 

A general investigation of the Vlllth group metals led to the discovery of much improved and often unusual efficiences (up to 100%) and selectivities with palladium(II) and rhodium(II) carboxylates. Some metal carbonyls (Rh6(C0)16 and Ru3(C0)12, VKC0)6, Mo(C0)6) [6] catalyze typical carbene reactions. More recently, new catalytic systems,(Rh(III) (porphyrin) VII [7], Co(III) (oxime) VIII [8]. ..) have been described. Their application in synthesis is however limited for different reasons such as the cost, the difficult synthesis of the complex or their lack of versatility. 

While major advances in the area of C-H functionalization have been made with catalysts based on rare and expensive transition metals such as rhodium, palladium, ruthenium, and iridium [7], increasing interest in the sustainability aspect of catalysis has stimulated researchers toward the development of alternative catalysts based on naturally abundant first-row transition metals including cobalt [8]. As such, a growing number of cobalt-catalyzed C-H functionalization reactions, including those for heterocycle synthesis, have been reported over the last several years to date (early 2015) [9]. The purpose of this chapter is to provide an overview of such recent advancements with classification according to the nature of the catalytically active cobalt species involved in the C-H activation event. Besides inner-sphere C-H activation reactions catalyzed by low-valent and high-valent cobalt complexes, nitrene and carbene C-H insertion reactions promoted by cobalt(II)-porphyrin metalloradical catalysts are also discussed. 

C-H alkylation and amination reactions involving metal-carbenoid and metal-nitrenoid species have been developed for many years, most extensively with (chiral) dirhodium(ll) carboxylate and carboxamidate complexes as catalysts [45]. When performed in intramolecular settings, such reactions offer versatile methods for the (enantioselective) synthesis of hetero- and carbocy-cles. In the past decade, Zhang and coworkers had explored the catalysis of cobalt(II)-porphyrin complexes for carbene- and nitrene-transfer reactions [46] and revealed a radical nature of such processes as a distinct mechanistic feature compared with typical metal (e.g., rhodium)-catalyzed carbenoid and nitrenoid reactions [47]. Described below are examples of heterocycle synthesis via cobalt(II)-porphyrin-catalyzed intramolecular C-H amination or C-H alkylation. 

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