Hatakeyama synthesis

Deacetoxylation of 128e gave erythrocarine [Eq. (6.101)]. Using a similar procedure, Hatakeyama succeeded in the total synthesis of erythravine ... 

The structurally-related 7-lactams salinosporamide A 1, omuralide 2 and lactacystin 3, of bacterial origin, inhibit proteasome activity, and so are of interest as lead compounds for the development of anticancer agents. Barbara . M. Potts of Nereus Pharmaceuticals in San Diego has reported (J. Med. Chem. 2005,48,3684) a detailed structure-activity studies in this series, and E.J. Corey of Harvard University has prepared (J. Am. Chem. Soc. 2005,127, 8974, 15386) several interesting structural analogues. Susumi Hatakeyama of Nagasaki University, building on previous work in this area, has reported (J. Org. Chem. 2004, 69,7765) a synthesis of 2 and 3 from Tris. 

Yoshikawa, M, Murakami, N, Inoue, Y, Hatakeyama, S, Kitagawa, I, A new approach to the synthesis of optically-active pseudo-sugar and pseudo-nucleoside — syntheses of pseudo-alpha-D-arabinofur-anose, (- -)-cyclaradine, and (-l-)-l-pseudo-beta-D-arabinofuranosyliiracil from D-arabinose, Chem. Pharm. Bull, 41, 636-638, 1993. 

The groups of Corey [63,64,65,66], Omura and Smith [67,68], and Baldwin [69] have reported the total synthesis of lactacystin (108) the starting materials of their syntheses are amino acids. The groups of Panek [70], Hatakeyama [71], Kanai and Shibasaki [72], and Jacobsen [73] have also reported the total synthesis of lactacystin (108). 

M. Nishizawa, H. Imagawa, E. Morikuni, S. Hatakeyama, and H. Yamada, Synthesis of cyclo-L-rhamnopentaose, Chem. Pharm. Bull., 42 (1994) 1365-1366. 

Hatakeyama, S., Satoh, K., Sakurai, K., and Takano, S., A synthesis of (-)-pyrenophorin using 4-DMAP-catalyzed ester exchange reaction of phosphonoacetates with lactols. Tetrahedron Lett., 28, 2717, 1987. 

Nishioka, T., Iwabuchi, Y, Irie, H., and Hatakeyama, S., Concise enantioselective synthesis of (-t)-aspicilin based on a ruthenium catalyzed olefin metathesis reaction. Tetrahedron Lett.. 39, 5597, 1998. Williams, D.R., and Clark, M.P., The macrocyclic domain of phorboxazole A. A stereoselective synthesis of the Cj-Cjj macrolactone. Tetrahedron Lett., 40, 2291. 1999. 

Very few efficient catalytic enantioselective versions of MBH reaction were known up to 1999 despite a considerable amount of efforts devoted to the field. A breakthrough came in 1999 when Hatakeyama and coworkers discovered that p isocupreidine (P ICD) is an efficient catalyst for the MBH reaction [11]. Meanwhile, the use of small organic molecules as catalysts to perform asymmetric transformations has received increasing attention over the past decade. Therefore, chiral multifunctional orga nocatalysts have also been developed rapidly to promote successful enantioselective MBH/aza MBH processes. This chapter mainly summarizes recent advances in the design and synthesis of small organic molecules for the enantioselective aza MBH reactions from 2000. On the basis of these enantioselective aza MBH reactions, a variety of chiral amines can be easily prepared under mild conditions. 

Baba K, Kaneko T, Hatakeyama R et al (2010) Synthesis of monodispersed nanoparticles functionalized carbon nanotubes in plasma-ionic liquid interfadal fields. Chem Commun 46 255-257... 

S23 K. Orito, T. Hatakeyama, M. Takeo, H. Suginome, M. Tokuda, Synthesis 1997, 23. 

S. Hatakeyama s C13 phosphonate Scheme 54) is treated in 5. K Ley s synthesis Scheme 55) with a different C7 aldehyde. The resulting C20 triene can be transformed into the 18-membered macrolide by intramolecular metathesis. The C7 aldehyde is accessible by a fairly lengthy series of reaction steps [111] starting from dimethyl (2/ ,3 )-tartrate. 

In recent years the discovery of novel methods of asymmetric synthesis has greatly increased the ability of organic chemists to synthesize optically active sugars. For example, the asymmetric epoxidation reaction discovered by Katsuki and Sharpless [142] was recently used as the key step in a synthesis of D-oleandrose 118 from divinyl carbinol 119 by Hatakeyama et al. [143]. An alternative approach to asymmetric synthesis of oleandrose was taken by Danishefsky et al. [144,32] in their synthesis of avermectin which is the first, and currently the only, reported total synthesis of an avermectin. The key step of this synthesis was a cyclocondensation reaction of optically active diene 121 with acetaldehyde catalyzed by the optically active Lewis acid (-h)-Eu(hfc)3 [145]. The resulting chiral pyrone was then elaborated to methyl-L-oleandroside 113. This was further converted to the disaccharide glycal 122 by a 4 step sequence in which glycoside formation was accomplished by iV-iodosuccinimide mediated addition of the alcohol to a glycal followed by tributyltin hydride... 

Subsequently, Hatakeyama et successfully employed this methodology for the synthesis of the important biologically active molecules epopromycin B (125), 2 -cpi-epopromycin B (126) and (-)-mycestericin E (127), which involved a p-ICD-catalyzed asymmetric MBH reaction as the key step (Scheme 2.62). 

On the basis of this work, Hatakeyama et al. have investigated the p-ICD-catalyzed MBH reaction of chiral iV-Boc-oi-amino aldehydes 140 and HFIPA (Scheme 2.67). The reaction proceeded smoothly without racemization and exhibited the match-mismatch relationship between the substrate and the catalyst, which was similar to that of the synthesis of epopromycin B from iV-Fmoc-L-leucinal with HFIPA. In the case of acyclic amino aldehydes. 

Very recently, an intramolecular cycloaldolization was employed successfully early in the synthesis of quinine (2) and quinidine (3) (97). Hatakeyama etal. used a (S)-12 catalyzed aldol reaction followed by in situ reduction of the aldol product with NaBBLj to obtain the diastereomers 99 and 100 in good yield and enantios-electivity (dr = 1 2). Followed by protection of the primary alcohol and oxidation of the secondary one, intermediate 101 with the desired configuration could easily be obtained. The intermediate 101 was then transformed into either 2 or the pseudoenantiomeric 3 by known methods (Scheme 23) (97). 

Another class of reaction for which chiral tertiary amines are privileged catalysts is the Morita-Baylis-Hillman type (477, 478). One of the first applications of Cinchona alkaloids to mediate an asymmetric Morita-Baylis-Hillman reaction in a natural product synthesis was reported by Hatakeyama et al. in 2001 (479). Using a stoichiometric amount of (3-isocupreidine (568), a stereoselective addition of hexafluoroisopropyl acrylate (569) to aldehyde 570 could be carried out in good yield and with excellent selectivity (99% ee) (Scheme 119). The chiral p-hydroxy ester 571 was converted further into the epoxide 572, a known intermediate in the synthesis of epopromycin B (573). Epopromycin B (573) is a plant cell wall... 

Iwabuchi Y, Furukawa M, Esumi T, Hatakeyama S (2001) An Enantio- and Stereocontrolled Synthesis of (-)-Mycestericin E via Cinchona Alkaloid-Catalyzed Asymmetric Baylis-Hillman Reaction. Chem Commun 2030... 

Sarkar SM, Wanzala EN, Shibahara S, Takahashi K, Ishihara J, Hatakeyama S (2009) Enantio- and Stereoselective Route to the Phoslactomycin Eamily of Antibiotics Formal Synthesis of (+)-Fostriecin and (+)-Phoslactomycin B. Chem Commun 5907... 

Hatakeyama S, Ochi N, Numata H, Takano S (1988) A new route to substituted 3-methoxy-carbonyldihydropyrans enantioselective synthesis of (-)-methyl elenolate. J Chem Soc Chem Commun 1988 1202-1204... 

Hirose S, Hatakeyama T, Hatakeyama H (1978) Synthesis and thermal analysis of polyethers related to lignin. Cell Chem Technol 12 713-720... 

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