Highly selective synthetic organic reactions utilizing cleavage of C-Cl bond

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1 Highly selective synthetic organic reactions utilizing cleavage of C- bond SmI 2 Reformatsky rg. Lett. 2008, 10, 5453.) C- C-C C- C-C C- C-- C- Chem. Lett. 2009, 38, Sc(Tf) 3 (Chem. Lett. 2010, 39, 194.) 6 -Methoxyretrojusticidin B Procumphthalide A ) (Synlett 2010, 15, 2275.) (6 -Methoxy-retrojusticidin B ) 5 -methoxy-retrochinensin 1) We developed a stereoselective synthesis of cyclopropane derivatives utilizing a highly stereoselective SmI 2 -promoted Reformatsky-type reaction and acylation of 1-chlorocyclopropanecarboxylic esters. The present method is a new avenue for the stereoselective synthesis of highly substituted cyclopropylcarbonyl compounds. Utilizing radical formylation and the present protocols, we achieved a highly stereoselective double-carbon elongation on the dichloro- carbon of gem-dichlorocyclopropanes. We also developed a stereoselective synthesis of cyclopropane derivatives utilizing a highly stereoselective SmI 2 -promoted C-silylation and alkylation of 1-chlorocyclopropane- carboxylic esters. Based on the fact that no -TMS-product was obatained, a SmI 2 -enolate might not be generated or should exist as a particular intermediate that can not react with TMS on oxygen atom. 2) We developed a novel synthesis of 1-aryl-1,2- dihydronaphthalene-3-carboxylic acid esters utilizing a Lewis acid-mediated regioselective ring-expansion of methyl (aryl- hydroxymethyl)cyclopropanecarboxylate. Application of the present method to a total synthesis of natural product is now being performed. 3) We achieved the first total synthesis of a novel (±)-6 -methoxyretrojusticidin B, which was proposed as procumphthalide A, utilizing regiocontrolled benzannulation of an aryl(aryl )-2,2-dichlorocyclopropylmethanol as the key step. 1H-NMR spectral data suggested that the structure of the synthesized product, 6 -methoxyretrojusticidin B, was inconsistent with that of natural procumphthalide A. The revised structural elucidation of natural procumphthalide A was concluded to be 5 - methoxyretrochinensin ,400, ,000 1,820, ,300, ,000 1,690, ,000, ,000 1,300, ,700,000 1,110,000 4,810,000

2 α rg. Lett. 2007, 9, 563. α J. Am. Chem. Soc. 2004, 126, )

3 C- Angew. Chem. Int. Ed. 2007, 46, R 4 sp 2 ~sp 3 C- C, Bu 3 SnR cat. AIBN or Allyl R 4 R3 CR Chem. Lett. 2007, 36, 62. Synthesis, 1996, 338) SmI 2 Reformatskyrg. Lett. 2008, 10, 5453.) SmI 2, HMPA R 4 CR R 4 R5 R 5 R 6 R = Me (R = Me) rg. Lett. 2008, 10, CR H R 6 (1) C- C-C C- C-C SmI 2 Chem. Lett. 2009, 38, 1078.)

4 SmI 2, HMPA R 4 CR R 5 X R 4 R 5 R = Me (R = Me) Chem. Lett. 2009, 38, (open access article). CR C- C- - C- Me Me Me Me Me Me Axial chirality Reported structure of Procumphthalide A Synlett 2010, 15, (J. Am. Chem. Soc. 2004, 126, 5358.) Procumphthalide A (Chem. Lett. 2010, 39, 194.) Ph C 2 Me H Sc(Tf) 3 or BF 3 įet Me 2 C 2 Ph Chem. Lett. 2010, 39, (open access article). Sc(Tf) 3 (6 -Methoxy-retrojusticidin B ) 5 -methoxy-retrochinensin First Total Synthesis of (±)-6'-Methoxyretrojusticidin B Using Regiocontrolled Benzannulation: structural Inconsistency with Procumphthalide A and Its Revision to 5'-Methoxyretrochinensin; Yoshida, E.; Yamashita, D.; Sakai, R.; Tanabe, Y.; and Nishii, Y. Synlett, 2010, 15, Me Me H Me Me H 2 C H Cyclogalgravin I Trilobatin A Lewis Acid-mediated Highly Regioselective Ring-expansion of Methl 2-Phenyl-1-(arylhydroxymethyl)cyclopropa necarboxylates; Yoshida, E.; Nishida, K.; Toriyabe, K.; Taguchi, R.; Motoyoshiya, J.; and Nishii, Y. Chem. Lett. 2010, 39, Me H Me H (Synlett 2010, 15, 2275.) Highly stereoselective C-Silylation and Alkylation of 1-Chlorocycropropanecarboxylic Ester Using SmI 2 ; Yoshida, E.; Nagano, T.; Motoyoshiya, J.; Nishii, Y. Chem. Lett. 2009, 38, Practical, general, and systematic method for optical resolution of gem-dihalo- and monohalocyclopropanecarboxylic acids utilizing chiral 1,1 -binaphtholmonomethyl ethers: Application to the synthesis of three chiral pesticides, Hiroaki Yasukochi,

5 Takayuki Atago, Akihiro Tanaka, Hidefumi Nakatsuji, Eri Yoshida, Akikazu Kakehi, Yoshinori Nishii and Yoo Tanabe, rg. Biomol. Chem., 2008, 6, , SmI 2 -Promoted Reformatsky-Type Reaction and Acylation of Alkyl 1-Chlorocyclopropanecarboxylates, Takao Nagano, Jiro Motoyoshiya, Akikazu Kakehi, Yoshinori Nishii, rg. Lett. 2008, 10, ( ) ;,,,,,, 90 (2010),, , A SmI 2 1- C- ;,,,,, 90 (2010), 2F7-10,, , A Yoshida, Jiro Motoyoshiya, 15th Iupac Symposium on rganometallic Chemistry Directed Towards rganic Synthesis (MCSIS), Jordanhill Campus, Glasgow, 28, July, SmI 2 Reformatsky ;,,, 89 (2009), 4G3-16,, , B 3-(α- )-2- Reformatsky ;,,,, 89 (2009), 2PC-013,, , gem- ;,,, 90 (2010), 2F7-12,, , A SmI 2 -Promoted Reformatsky-Type Reaction of Alkyl 1-Chlorocyclopropanecarboxylates; Yoshinori Nishii, Takao Nagano, Eri

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