Hydrophosphonylation of imines

3 For selected excellent contributions of metal-catalyzed asymmetric cyanations, see (a) M. S. Sigman, 

Sigman, E. N. Jacobsen, Book of Abstracts, 216th ACS Meeting, Boston, August 23-27, 1998. 

15 Previously, some Strecker reactions were conducted in the presence of optically active bases and acids, but did not give asymmetric induction, see Y. Ogata, A. Kawasaki,/. Chem. Soc B 1971, 325-329. 

17 Such type of approach has been reported recently when using Zr based chiral catalysts, see ref. [3d], 

20 For selected asymmetric metal-catalyzed Mannich-type reactions, see (a) H. Fujieda, M. Kanai, T. Kambara, A. Iida, K. Tomioka, /. Am. Chem. Soc. 1997, 339, 2060-2061 (b) 

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Shibasaki reported the first catalytic asymmetric hydrophosphonylation of imines in 1995 (Scheme 5-45) using heterobimetallic LLB-type catalysts. 

Based on prior results where Ricci used Cinchona alkaloids as phase-transfer-catalysts, the group proceeded to look at hydrophosphonylation of imines [48], Employing the chiral tertiary amine as a Brpnsted base, a-amino phosphonates products were synthesized in high yields and good selectivities. 

The asymmetric catalytic hydrophosphonylation is an attractive approach for the synthesis of optically active a-amino phosphonates [84]. The first example of this type of reaction was reported by the Shibasaki group in 1995 using heterobimetal-lie lanthanoid catalysts for the hydrophosphonylation of acyclic imines [85a]. This concept has been extended to the asymmetric synthesis of cyclic a-amino phosphonates [85b—d]. Very recently, the Jacobsen group developed the first organocatalytic asymmetric hydrophosphonylation of imines [86], In the presence of 10 mol% of thiourea-type organocatalyst 71, the reaction proceeds under formation of a-amino phosphonates 72 in high yield (up to 93%) and with enantioselectivity of up to 99% ee [86], A selected example is shown in Scheme 5.42. Di-o-nitrobenzyl phosphite 70 turned out to be the preferred nucleophile. 

Hydrocyanation of imines [5.1] Mannich reaction [5.2] Hydrophosphonylation of imines [5.5]... 

A BINOL-derived phosphoric acid derivative has been used as a catalyst in the enantioselective synthesis of a-amino phosphonates via hydrophosphonylation of imines with diisopropyl phosphite.82... 

I. Catalytic, asymmetric hydrophosphonylation of imines promoted by the lanthanoid-potassium-BINOL catalyst (LnPB)... 

The second part of the chapter deals with several kinds of asymmetric reactions catalyzed by unique heterobimetallic complexes. These reagents are lanthanoid-alkali metal hybrids which form BINOL derivative complexes (LnMB, where Ln = lanthanoid, M = alkali metal, and B = BINOL derivative). These complexes efficiently promote asymmetric aldol-type reactions as well as asymmetric hydrophosphonylations of aldehydes (catalyzed by LnLB, where L = lithium), asymmetric Michael reactions (catalyzed by LnSB, where S = sodium), and asymmetric hydrophosphonylations of imines (catalyzed by LnPB, where P = potassium) to give the corresponding desired products in up to 98% ee. Spectroscopic analysis and computer simulations of these asymmetric reactions have revealed the synergistic cooperation of the two different metals in the complexes. These complexes are believed to function as both Brpnsted bases and as Lewis acids may prove to be applicable to a variety of new asymmetric catalytic reactions.1,2... 

Figure 35. Proposed catalytic cycle for hydrophosphonylation of imines.

Scheme 6.11 Phosphoric acid-catalyzed hydrophosphonylations of imines.

Akiyama T, Morita H, Itoh J, Fuchibe K (2005a) Chiral Brpnsted acid catalyzed enantioselective hydrophosphonylation of imines asymmetric synthesis of alpha-amino phosphonates. Qrg Lett 7 2583-2585 Akiyama T, Saitoh Y, Morita H, Fuchibe K (2005b) Enantioselective Mannich-type reaction catalyzed by a chiral Bronsted acid derived from TADDOL. Adv Synth Catal 347 1523-1526... 

Thiourea-catalysed enantioselective hydrophosphonylation of imines (370) using phosphite (371) provides a general and convenient route to a wide range of highly enantiomerically enriched a-amino phosphonates (372). The deprotection of these products yields the corresponding a-amino phosphonic acids (373) (Scheme 95). ... 

Scheme 10. LnPB-catalyzed asymmetric hydrophosphonylation of imines.

Figure 7. Influence of the catalytic amount on asymmetric hydrophosphonylation of imine 59.

Some of the metal-based catalysts used in the asymmetric hydrophosphonylation of aldehydes (see Section 6.4) can also be applied to the phosphonylation of imines. For instance, Shibasaki s heterobimetallic BINOL complexes work well for the catalytic asymmetric hydrophosphonylation of imines. In this case lanthanum-potassium-BINOL complexes (6.138) have been found to provide the highest enantioselectivities for the hydrophosphonylation of acyclic imines (6.139). The hydrophosphonylation of cyclic imines using heterobimetallic lanthanoid complexes has been reported. Ytterbium and samarium complexes in combination with cyclic phosphites have shown the best results in the cases investigated so far. For example, 3-thiazoline (6.140) is converted into the phosphonate (6.141) with 99% ee using ytterbium complex (6.142) and dimethyl phosphite (6.108). The aluminium(salalen) complex (6.110) developed by Katsuki and coworkers also functions as an effective catalyst for the hydrophosphonylation of both aromatic and aliphatic aldimines providing the resulting a-aminophosphonate with 81-91% ee. ... 

An efficient organocatalytic enantioselective hydrophosphonylation of imines to numerous enantiomerically enriched (R)-amino phosphonates was reported by Pettersen and Fini. The enantioselectivity was found to be N-protecting group and solvent depended. Thus, replacing Ts with Boc raised the ee of the product from 48 to 68% and replacing toluene with xylene further increased the ee to an acceptable 80% (for Ar = Ph). Quinidine yielded the opposite enantiomer in considerably lower ee (45%), but unfortunately, unlike quinine (Scheme 15.3), was not tested under optimised conditions and with a representative selection of aromatic imines. 

Scheme 15.5 Hydrophosphonylation of imines with diphenyl phosphite.

For selected pioneering examples, see (a) D. Uraguchi, K. Sorimachi, M. Terada, J. Am. Chem. Soc. 2004, 126, 11804-11805. Organocatalytic asymmetric aza-Friedel-Crafts alkylation of furan. (b) T. Akiyama, H. Morita, J. Itoh, K. Fuchibe, Org. Lett. 2005, 7, 2583-2585. Chiral Br0nsted acid catalyzed enantioselective hydrophosphonylation of imines asymmetric synthesis of a-amino phosphonates. 

It worth to mention that despite the importance of the Kabachnik-Fields reaction, stereoselective versions for the synthesis of enantioenriched a-aminophosphonates are scarce [212, 213], and only few enantioselective examples have been published to date (for reviews on enantioselective catalytic direct hydrophosphonylations of imines, see Refs. [162a-c]). Organocatalytic examples use well-known chiral binol-derived phosphoric acid organocatalysts (Fig. 12.6,80 and 81) [214], and regarding metal catalysis, chiral scandium(III)-A,A -dioxide and... 

This kind of heterobimetallic complexes are excellent catalysts for a wide range of reactions, including epoxidation of enones, hydrophosphonylation of imines and aldehydes, and a range of asymmetric C-C bond formation reactions, involving Michael addition reaction, Diels-Alder reaction, aldol and nitroaldol reaction, etc. The alkaU metal has a profoimd effect on the catalytic property of these compounds. 

The hydrophosphonylation of imines bearing a variety of organic fragments has been reported under a range of conditions. Even crowded substrates are typically responsive to the addition reaction. As an example of this, an anthracene bearing imine has been successfully functionalized using secondary phosphites (Scheme 4.87) [160]. Simply refluxing the reaction mixture for 14h afforded moderate yields of the a-aminophosphonates. 

For activation of more unconventional substrates in the asymmetric addition to imines, Ricci and coworkers [13d] investigated the utility of asymmetric phospho-nylation. The hydrophosphonylation of imines was achieved to provide a-amino... 

The Kabachnik-Fields reaction is a three-component hydrophosphonylation of imines formed in the reaction mixture from carbonyl compounds and amines [75]. In 2008, List and coworkers reported on such a reaction catalyzed by chiral phosphoric acids that combines a dynamic kinetic resolution with the concomitant generation of a new stereogenic center (Scheme 42.30). The resolution is possible when chiral racemic aldehydes 135 are used. This is because the imine formed in the first step of the reaction is in equilibrium with its achiral enamine tautomer, thereby racemizing the starting material continuously. Since one of the two enantiomers is selectively activated by the chiral phosphoric acid catalyst, the addition of phosphite 136 affords the exclusive formation of one diastereomer. All phos-phonate products 137 were obtained with good yields and moderate to excellent diastereo- and enantioselectivity [76]. 

More recentiy, aluminum salalen complex 112 was used by Katsuki et al. for enantioselective hydrophosphonylation of imines." The reaction has a broad scope, giving access to a variety of phosphonic amino acids analogs, and in most cases, products with high ee could be obtained (Scheme 47.26). 

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