88288-20-4

Upstream product

• 117965-38-5 <4.3.2>propell-3-en-2-one 
• 118558-77-3 1-cyclobutylidenespiro<3.3>heptane 
• 38229-67-3 Tricyclo<4.3.2.0^1,6>undecan-2-one 
• 117965-37-4 <3.3.3>propell-7-en-2-one 
• 108572-91-4 dispiro<2.1.3.3>undecane-4-one 
• 102794-89-8 dispiro<3.0.3.3>undecane-9-one 
• 118558-78-4 (5R*)-dispiro<3.0.4.2>undecane-6-one 
• 160246-10-6 (5R*)-6-(4-nitrobenzenesulfonimido)dispiro<3.0.4.2>undecane 
• 160246-07-1 9-(4-nitrobenzenesulfonimido)dispiro<3.0.3.3>undecane 
• 102794-86-5 10,10-dichlorodispiro<3.0.3.2>decane-9-one 
• 102794-87-6 dispiro<3.0.3.2>decane-9-one 
• 160246-06-0 9-methylenedispiro<3.0.3.2>decane 
• 160246-11-7 dispiro<3.1.3.2>undecane-5-one 
• 38229-67-3 Tricyclo<4.3.2.0^1,6>undecan-2-one 

Downstream Products

• 111917-14-7 2-methylenetricyclo<3.3.3.0>undecane 

Relevant academic research and scientific papers

SYNTHESIS AND REARRANGEMENT OF FUNCTIONALIZED DISPIROUNDECANES A NEW ENTRY TO PROPELLANES

The functionalized dispiroundecanes 6 and 7 undergo cascade rearrangements to yield the propellanes 15 and 11, respectively.The formation of 15 proceeds via the bicyclic enone 16.

TOWARDS A SYNTHESIS OF (+/-)MODHEPHENE VIA CASCADE REARRANGEMENT: SYNTHESIS AND REARRANGEMENT OF DISPIROUNDECANES TO PROPELLANES

The dispiroundecanes 2 and 6 undergo cascade rearrangements yielding the propellanes 3 and 7, respectively.The rearrangement of 6 proceeds regiospecifically and renders 9 a promising candidate for a direct conversion to (+/-)modhephene 10.

SYNTHESIS AND REARRANGEMENT OF DISPIRO-, DISPIRO- AND DISPIROUNDECANES - NEW ENTRIES TO PROPELLANES

The dispiroketones 4-6 have been synthesized and rearranged by treatment with acids yielding the bicyclic enone 36 under kinetic control and the propellane 37 under thermodynamic control.The corresponding alcohols 10-12 all yield the propellane 41.The rearrangement of -12 to -41 proceeds stereospecifically and points to dispirane 42 as potential precursor of(+/-)modhephene 43.Likewise, dispiranes 44 and 46 are potential precursors of (+/-)-isocomene 45.

SYNTHESIS AND REARRANGEMENT OF FUNCTIONALIZED DISPIROUNDECANES - PREFERRED C4-C5 OVER C3-C4 RING ENLARGEMENTS

The functionalized dispiroundecanes 9 and 8 undergo cascade rearrangements to yield the bi- and tricyclic systems 10, 11, 12 and 3, respectively.The rearrangements proceed via an initial enlargement of the four-membered ring.

Acid-Catalyzed Rearrangement of Propellanones

The acid-catalyzed rearrangement of propellanones (m = 3-5, n = 3,4) was studied to ascertain the effect of ring size on the mode of rearrangement.Propellanones 9 and 10, containing a five-membered cycloalkanone ring, did not rearrange.Propellanones containing a six- or seven-membered cycloalkanone ring (11-14) rearranged smoothly to cyclopentanones 17a, 18, and 19 in a nonnucleophilic medium.In the presence of a nucleophile, the course of the rearrangement depended on wether the third cycloalkane ring contained three, four, or five carbon atoms.Thus propellanones 11 and 14 rearranged to (1S*,5R*,6S*)-tricyclo1,5>undecane derivatives 20a,b and -tricyclo1,6>dodecane derivatives 22a and 23 by an unusual 1,2 alkyl shift of the central propellane bond followed by nuleophilic attack.The structures of 20a,b, 22a, and 23 were established by chemical transformations (Scheme II).The stereochemistry of methyl substituents on the cyclobutane ring of dimethylpropellanones 15 and 16 influenced the course of rearrangement in the presence of a nucleophile.