Total synthesis and stereochemistry of (+)-phyllanthocindiol

Abstract

The total synthesis of (+)-phyllanthocindiol starting with (S)-(+)-3-hydroxy-2 -methylpropanoic acid and (S)-(-)-perilla aldehyde is reported. The totally enantioselective sequence elucidated the relative and absolute stereochemistry of (+)-phyllanthocindiol.

Synthesis of Optically Active Bifunctional Building Blocks through Enantioselective Copper-Catalyzed Allylic Alkylation Using Grignard Reagents

“…Thus, treatment of olefin 2a with PdCl 2 (10 mol %) and CuCl (2 equiv) under an O 2 atmosphere provided β-hydroxyketone 4a in 86% yield. This ketone has been applied in the total syntheses of the C 1 −C 25 segment of spirastrellolide A, the octalactins A and B, (+)-miyakolide, (−)-botryococcene, and also (+)-phyllanthocin and (+)-phyllanthocindiol . By carrying out an ozonolysis/NaBH 4 reduction protocol, 2a was converted into the monoprotected 1,3-diol 5a .…”

Practical TEMPO-Mediated Oxidation of Alcohols using Different Polymer-Bound Co-Oxidants

“…Aldehydes 12 -16, ketones 20 -22, 27, 28 and 30 as well as carboxylic acids 35 -41 are described in the literature or are commercially available. The spectroscopic and physical data of aldehydes 15 [29] and 16, [30] of ketones 27 [31] , 28, [32] and of carboxylic acids 39 [33] 40 [34] and 41 [35] are listed in the literature.…”

Lewis Base–Brønsted Acid–Enzyme Catalysis in Enantioselective Multistep One‐Pot Syntheses

“…[1][2][3] In recent advances it was demonstrated how elegant advantages of the individual catalytic steps can be exploited without the need for extensive purification, long hands-on times or large amounts of solvents.S ometimes combined approaches even turn out to be superior to individual steps by providing higher overall yields or avoiding the direct handling of certain troublesome materials.N aturally,h owever,t hose potentially fruitful endeavors bear challenges in orchestrating as uitable arrangement of reagents,catalysts and conditions to prevent not only undesired side reactions or decomposition of compounds,but also especially the inactivation of catalysts. [4][5][6][7][8][9][10][11][12][13] Thefocus of the present study is on a-methylated ketones 1 [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] and diols 2, [32][33][34][35][36][37][38][39][40] which are used extensively in natural product syntheses.O ver decades,t hey not only proved indispensable for finding and examining new pharmacologically active agents,but also for elucidating the mode of action of established blockbusters ranking among the most important drugs by sale.…”

“…The focus of the present study is on α‐methylated ketones 1 [ 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 ] and diols 2 ,[ 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 ] which are used extensively in natural product syntheses. Over decades, they not only proved indispensable for finding and examining new pharmacologically active agents, but also for elucidating the mode of action of established blockbusters ranking among the most important drugs by sale.…”