검색 상세

(+)-Petromyroxol and (+)-Isopetromyroxol via Highly Stereodivergent Intramolecular Amide Enolate Alkylation

  • 임성주 (Lim Seongju, 아주대학교 일반대학원)

초록/요약

We have accomplished the total synthesis of C14 tetrahydrofuranoids (+)-petromyroxol (1a) and (+)-isopetromyroxol (1b) employing the highly stereoselective construction of ,'-trans-THF 3a and ,'-cis-THF 3b using a highly stereodivergent IAEA reaction of a common cyclization substrate -tosyl -alkoxy amide 4 in a nonchelate-controlled and chelate-controlled manner, respectively. In addition, our direct ketone synthesis/L-Selectride reduction sequence has been efficiently applied to the incorporation of the stereoselective introduction of the C(9)−C(14) appendage at C(8) in the natural products. Finally, the choice of benzyl crotonate as a counterpart of in cross metathesis reaction could enable the process of the global deprotection of benzyl ether and benzyl ester by catalytic hydrogenolysis concomitant with hydrogenation of the ,-unsaturated ester moiety in a highly efficient manner.

more

목차

Ⅰ. Introduction 1
1. Previous Synthesis of Petromyroxol and Iso-petromyroxol 3
A. Boyer’s Synthesis of (+)-1a 4
B. Ramana Synthesis of (+)-1a and (‒)-1b 5
C. Pandey’s Synthesis of (+)-1a 6
D. Kumar’s Synthesis of (+)-1a 7
E. Reddy’s Synthesis of (+)-1a 8
F. Fernandes’ Synthesis of (+)-1a 9
Ⅱ. Results and Discussions 10
1. Total Synthesis of C14 Tetrahydrofuranoids (+)-Petromyroxol (1a) and (+)-Isopetromyroxol (1b) 10
1. Retrosynthetic Plan for (+)-Petromyroxol and (+)-Isopetromyroxol 12
2. Construction of Key 5,8-trans- and 5,8-cis-THF Intermediates 2a and 2b 14
2. Completion of the Total Synthesis of (+)-Petromyroxol (1a) and (+)-Isopetromyroxol (1b) 18
Ⅲ. Conclusion 22
Ⅳ. Experimental 23
Ⅴ. References 66

more
반출 Meta View 목록