Development of progressive asymmetric syntheses of alkaloid based on construction of heteroatom bridged compounds

2014 Fiscal Year Final Research Report

• Project/Area Number: 24550116
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Shinshu University
• Principal Investigator: SUGA Hiroyuki 信州大学, 学術研究院工学系, 教授 (60211299)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Keywords: 付加環化 / ジアゾ化合物 / キラルルイス酸 / エナンチオ選択性 / 生理活性 / カルボニルイリド / アゾメチンイリド

Outline of Final Research Achievements

Highly enantioselective 1,3-dipolar cycloaddition reactions between several 3-(2-alkenoyl)-2-oxazolidinones and cyclic carbonyl ylides that were generated from N-diazoacetyl lactams have been developed. Reactions of N-diazoacetyl lactams that possess 5-, 6-, and 7-membered rings were transformed to the corresponding epoxy-bridged indolizidines, quinolizidines, and 1-azabicyclo[5.4.0]undecanes with good to high enantioselectivities. The epoxy-bridged indolizidines were revealed to be important intermediates for the synthesis of optically active hydroxylated indolidizine derivatives. The cycloaddition reactions between N-methylindoles and 6-membered cyclic carbonyl ylides derived from 1-diazo-5-aryl-2,5-pentanedione precursors also showed high enantioselectivities along with relatively good exo-selectivities. Similar asymmetric cycloadditions of cyclic azomethine ylides derived from diazo imine derivatves have been developed to afford excellent to good enantioselectivities.

Free Research Field

有機合成化学