Synthetic Applications of the Carbonyl Generating Grob Fragmentation

Abstract

Since 1996, he has been a full professor at the University of Vienna. His main research interests lie in the total synthesis of structurally and physiologically interesting natural products. Scheme 1. Early Fragmentation of Carbocation Observed Scheme 2. Fragmentation of Carbocation into Olefin and Ketone Scheme 3. Eschenmoser's Pioneering Work on Fragmentations Scheme 4. Spontaneous Fragmentation of β-Bromo Acid 19

Crystal structure of (2-(2-chlorophenyl)-5-ethyl-1,3-dioxan-5-yl)methanol hemihydrate, C13H17ClO3 · 0.5 H2O

“…The synthesis of 1,3-dioxane compounds was mainly applied from aldol reaction through hydroxy containing polyfunctional group with aldeyde (ketone) [3]. 2,2-Bis(hydroxymethyl) butanol, which has typical neoamyl group, is a common chemical product [4][5][6][7].…”

Progress in the Total Syntheses oftrans-Hydrindane-Containing Terpenoids

“…在有机反应中, Grob 碎片化反应是构建酮羰基的有 效方法之一 [39] . 印度科学普及协会 Mukherjee 小组 [40] 利 用该反应来构建 zizaene 的反式六氢茚满酮结构(Scheme [41] .…”

One‐Step Stereospecific Strategy for the Construction of the Core Structure of the 5,11‐Methanomorphanthridine Alkaloids in Racemic as well as in Optically Pure Form: Synthesis of (±)‐Pancracine and (±)‐Brunsvigine

“…[39] Attempted deprotection of the acetal moiety of 46 under a variety of acidic conditions (3 n HCl/THF/H 2 O, oxalic acid/THF/H 2 O) prior to executing the HWE reaction resulted only in the rearranged product 49 in 68 % yield along with some unidentifiable product. The formation of 49 may be rationalized by invoking the intermediacy of the thermodynamic enol ether followed by rearrangement by Grobtype fragmentation [40] or by the azetidium salt intermediate 55, as shown in Scheme 11. This rearranged skeletal product supports our earlier observation for the formation of 34.…”