120950-84-7

Upstream product

• 5323-87-5 3-Ethoxycyclohex-2-en-1-one 
• 2695-47-8 6-Bromo-1-hexene 
• 120950-82-5 3-<4-pentenyl-6-(trimethylsilyl)>-cyclohex-2-en-1-one 
• 30043-41-5 (hex-5-enyl)magnesium bromide 
• 504-02-9 1,3-cylohexanedione 
• 629-03-8 1 ,6-dibromohexane 

Downstream Products

• 1440419-47-5 5-(hex-5-en-1-yl)-5-(nitromethyl)cyclohex-2-enone 
• 1440419-51-1 C₂₈H₃₃NO₃S 
• 1440419-49-7 N-{[7-(hex-5-en-1-yl)-1,4-dioxaspiro[4.5]dec-8-en-7-yl]methyl}-1-(4-methoxyphenyl)methanamine 
• 1440419-50-0 S-phenyl [(7-(hex-5-en-1-yl)-1,4-dioxaspiro[4.5]dec-8-en-7-yl)methyl](4-methoxybenzyl)carbamothioate 
• 1440419-52-2 S-phenyl [(1-(hex-5-en-1-yl)-5-oxocyclohex-3-en-1-yl)methyl](4-methoxybenzyl)carbamothioate 
• 1440419-46-4 3-(hex-5-en-1-yl)-3-(nitromethyl)cyclohexanone 

Relevant academic research and scientific papers

Catalytic Asymmetric Total Synthesis of Macrocyclic Marine Natural Product (–)-Haliclonin A?

We describe the full details of our total synthesis of haliclonin A, a macrocyclic natural product suggested to originate from a common biosynthetic intermediate as sarain A. Central to our synthetic route is the strategic employment of nitromethane for several purposes: (1) as an umpolung surrogate of an aminomethyl group; (2) as an ideal nucleophile for the highly enantioselective catalytic asymmetric conjugate addition to forge the challenging all-carbon quaternary stereogenic center that was used to induce the formations of all other chiral centers of the molecule; and (3) as a C1N1 building block to form the 3-azabicyclo[3.3.1]nonane framework. The realization of this strategy relied on the development of a novel organocatalytic asymmetric conjugate addition of nitromethane to 3-alkenyl cyclohex-2-enone, and the first Pd-promoted intramolecular coupling of a thiocarbamate moiety onto an electron-deficient alkene (enone) to form the 3-azabicyclo[3,3,1]nonane core. The synthesis also features a SmI2-mediated intermolecular reductive coupling of an enone with an aldehyde, ring-closing alkene and alkyne metathesis reactions to build the two aza-macrocycles, and an unprecedented direct transformation of enol into enone.

Toward the total synthesis of haliclonin a: Construction of a tricyclic substructure

Three keys to success: A concise method for the construction of a tricyclic substructure (2) of haliclonin A (1) in racemic form is described (see figure). This synthesis features a new Pd-mediated chemoselective carbonyl-enone coupling reaction, an organ

Photoreactions of Enones with Amines - Cyclization of Unsaturated Enones and Reductive Ring Opening by Photoinduced Electron Transfer (PET)

Photolysis of the unsaturated enones 1 yields cycloaddition products 2 and 3 with varying regioselectivity.Under electron transfer conditions (PET) spirocyclic products 4 are formed.The straight cycloaddition products 2b, c, f are converted to the spirocyclic products 4b, c, f under the same reaction conditions.The cyclobutane 5 and cyclopropane 11 also undergo this new reductive ring opening reaction, while the stabilized system 7 is converted to reduced ring-enlarged triquinane 10 which may be interesting in natural product synthesis. - Irradiation of 2-cyclohexen-1-one (14) in the presence of N,N-dimethylallylamine (15) leads to the decahydroisoquinoline 18.A mechanism involving radical intermediates is discussed. Key Words: Photoinduced electron transfer / Cyclization / Ring opening / Enones

STEREOSELECTIVE CYCLIZATION OF ALLYLSILANES AND -STANNANES

The syntheses and additions of allylsilanes, and -stannanes to enones and dienones forming spiro- and fused-bicyclic products are described.The stereoselectivity observed is dependent on the Lewis acid used.The tin terminator reverses the stereoselectivit