THANK FOR ALL OF YOU
J. Am. Chem. Soc, 2006, 128, 12658–12659
IV Summary
Described herein is an improved direct procedure for sulfenylation of diketopiperazines and its application to the synthesisof the bismethylthio- and epidithiodiketopiperazine structural motifs, as exemplified by the total synthesis of epicoccin G (1) . Employing endoperoxide intermediates,the described chemistry also demonstrates the applicability of the Kornblum DeLaMare rearrangement in total synthesis and should facilitate the construction of other members of the dithiodiketopiperazine class of compounds , natural or designed, for biological investigations.
J. Am. Chem. Soc. 2011, 133, 8150–8153.
Ⅰ
Background
Ⅱ Retrosynthetic Analysis III Synthetic Strategy IV Summary
About the natural products
Exserohilum rostratum
The original 1951 publication concerned the conversion of potassium t-butyl peroxide and 1-phenylethyl bromide to ultimately benzophenone and tbutanol with piperidine as the base:
J. Am. Chem. Soc, 1951,73, 880 – 881
The Kornblum–DeLaMare rearrangement can be carried out as an asymmetric reaction with a suitable chiral amine such as sparteine or a cinchona alkaloid.
O
54%
O Boc t-butoxycarbonyl
92%
51%
N N DBU
86%
77%
O O BOP-Cl O P N N O Cl O
90%
69%
Si
N
Si
Na NaHDMS
6பைடு நூலகம்%
18"
32.5% 34% 24%
52%
86%
51%
The Kornblum–DeLaMare rearrangement is a rearrangement reaction in which a primary or secondary organic peroxide is converted to the corresponding ketone and alcohol under base catalysis.
Against human colon carcinoma
Exserohilum holmii
Antibacterial and antifungal activity
Epicoccum nigrum
Anti-HIV activity
Ⅱ Retrosynthetic Analysis
III Synthetic Strategy