64884-88-4

Upstream product

• 119825-50-2 1-(ethoxycarbonyloxy)-2-cyclohexene 
• 123-38-6 propionaldehyde 
• 1521-51-3 rac-3-bromocyclohexene 
• 112520-99-7 tributyl(cyclohex-2-en-1-yl)stannane 
• 110-83-8 cyclohexene 
• 4545-18-0 N'-cyclohexylidene-4-methylbenzene-1-sulfonohydrazide 

Downstream Products

• 103984-64-1 3-cyclohex-2-enylpentan-3-ol 

Relevant academic research and scientific papers

The formation of 7-oxabicyclo[4.2.0]octanes and 6-oxabicyclo[3.2.1]octanes via cationic iodocyclization

Several 2-cyclohexenemethanol derivatives were subjected to cationic iodocyclization. Two product types were formed: the fused 7-oxabicyclo[4.2.0]octane, and the bridged 6-oxabicyclo[3.2.1]octane. The degree of substitution in the alkenol determined the ratio of the products, with aromatic substituents leading to the formation of the fused system as the major product.

Efficient synthesis of 7-, 8- and 9-membered cyclic allyltitanium compounds and their stereoselective addition reaction with aldehydes and imines

Reaction of 7-, 8- and 9-membered cyclic allylic compounds 2 with (η2propene)Ti(O-i-Pr)2 (1) via an oxidative addition pathway provides the corresponding allylic titanium compounds, which, in turn, react with aldehydes and imines stereoselectively, thus providing an efficient and stereoselective method for synthesizing cycloalkenes having a side chain at the allylic position.

Formation of homoallyl alcohols and 4-chlorotetrahydropyrans from allyl-stannanes, aldehydes and TiCl4 or Cp2TiCl2

Reaction between Bu3SnCHR1CH=CHR2 (1; R1 = H, R2 = H or Me; R1, R2 = (CH2)3) and EtCHO in the presence of TiCl4 or Cp2TiCl2 are reported.The compound, Cp2TiCl2, has been found to be an effective Lewis acid catalyst for the allylation of EtCHO using 1 (R1 = H, R2 = Me) and 1 (R1, R2 = (CH2)3) in CH2Cl2 or Et2O solutions at -78 deg C; the products after hydrolysis are homoallyl alcohols with stereo- and regio-selectivities different from those found for TiCl4- reactions.Reactions with an excess of EtCHO in the presence of TiCl4 give 4-Cl-3-R1-5-R2-2,6-2Et-tetrahydropyrans (2) via insertions of a second EtCHO into the metal-O bond of the initially produced homoallyl alcoholate: the trans-2 compounds are obtained from threo-EtCH(OM')CHR2CH=CHR1 and cis-2 from erythro-EtCH(OM')CHR2CH=CHR1 (e.g., M' = TiCl3).

Comparison of the allylation reactions of aldehydes using allylstannanes with boron trifluoride etherate and boron trichloride

Reactions between allylstannanes, R2CH=CHCHR1SnBu3 (R1 = R2 = H (4); R1 = H, R2 = Me (5); R1R2 = (CH2)3 (6) and aldehydes, RCHO (e.g.R = Et) in the presence of BF3OEt2 in CH2Cl2 at -78 deg C produce stereoselectively erythro-RCH(OH)CHR2CH=CHR1 (with one equivalent RCHO) and 4-OH-3-R1-5-R2-2,6-R2-tetrahydropyrans (with an excess of RCHO).In contrast, when BCl3 is used in place of BF3OEt2 the reactions give mixtures of chlorinated alkenes (both homoallyl chlorides and allyl chlorides) and 4-Cl-3-R1-5-R2-2,6-R2-tetrahydropyrans (3; X = Cl).Thus 5, EtCHO and BCl3 (all equimolar) provide EtCHClCH2CH=CHMe (51percent, (E) + (Z)), EtCHClCHMeCH=CH2 (7percent, erythro + threo), EtCH2CH=CH-CHMeCl (30percent, (E) + (Z)) and 3 (12percent, X = Cl); with EtCHO (2.2 equivalents). 3 (X = Cl; cis/trans = 70/30) becomes the sole product.The product, erythro-EtCHClCHCH=CH(CH2)2CH2 (97percent) was produced from equimolar EtCHO, BCl3 and 6; with excess EtCHO (2.2 equivalents), 9-Cl-2,4-Et2-cis-3-oxabicyclononane (17percent; cis/trans = 45/55) and erythro-EtCHClCHCH=CH(CH2)2CH2 (78percent) were obtained.

ALLYLSTANNATION. XI. A NEW CONVENIENT METHOD FOR THE SYNTHESIS OF 9-CHLORO-2,4-DIETHYL-cis-3-OXABICYCLONONANE

trans and cis-9-chloro-2,4-diethyl-cis-3-oxabicyclononane in the ratio 75:25 can be prepared via allylstannation by reacting cyclohex-2-enylbutyltin dichloride with propionaldehyde.