138832-36-7

Upstream product

• 4224-69-5 methyl 2-(bromomethyl)propenoate 
• 100-52-7 benzaldehyde 
• 74-97-5 chlorobromomethane 
• 922-67-8 propynoic acid methyl ester 
• 15484-46-5 methyl 2-hydroxymethylacrylate 

Downstream Products

• 36057-38-2 methyl (S)-2-methyl-4-oxo-4-phenylbutanoate 
• 26613-71-8 4-phenyl-2-methylenebutyrolactone 
• 35630-42-3 3-methylene-4-phenyldihydrofuran-2(3H)-one 

Relevant academic research and scientific papers

Isatin Derived Spirocyclic Analogues with α-Methylene-γ-butyrolactone as Anticancer Agents: A Structure-Activity Relationship Study

Design, synthesis, and evaluation of α-methylene-γ-butyrolactone analogues and their evaluation as anticancer agents is described. SAR identified a spirocyclic analogue 19 that inhibited TNFα-induced NF-?°B activity, cancer cell growth and tumor growth in an ovarian cancer model. A second iteration of synthesis and screening identified 29 which inhibited cancer cell growth with low-?M potency. Our data suggest that an isatin-derived spirocyclic α-methylene-γ-butyrolactone is a suitable core for optimization to identify novel anticancer agents.

Factors influencing the cytotoxicity of α-methylene-γ-hydroxy esters against pancreatic cancer

A systematic study to identify the factors influencing the cytotoxicity of α-methylene-γ-hydroxy esters against three pancreatic cancer cell lines (Panc-1, MIA-PaCa-2, and BxPC-3) has established that, in addition to Michael acceptor abilities, the possibility to lactonize to α-methylene-γ-butyrolactones is as important. The substitution pattern and the number of carbons between the hydroxy and ester moieties also influence the bio-activity.

Diastereoselective synthesis of α-(aminomethyl)-γ-butyrolactones via a catalyst-free aminolactonization

An auto-catalytic domino reaction, presumably involving an aza-Michael reaction, proton transfer, and lactonization, furnishing α-(aminomethyl)-γ-butyrolactones in near quantitative yields and excellent diastereoselectivity is described.

Highly diastereoselective hydrostannylation of allyl and homoallyl alcohols with dibutyl(trifluoromethanesulfoxy)stannane

Dibutyl(trifluoromethanesulfoxy)stannane (Bu2Sn(OTf)H, 1a) was found to be very valuable for highly diastereoselective homolytic hydrostannylation of allyl and homoallyl alcohols. α,β-Disubstituted allyl alcohols and α,γ-disubstituted homoallyl alcohols were converted into γ- and δ-stannylated alcohols with high 1,2-syn and 1,3-syn diastereoselectivity, respectively. The origin of the stereochemical outcomes can be rationalized by conformational fixation of the intermediary β-stannylalkyl radical by coordination of the hydroxy group to the Lewis acidic tin center. Copyright

Indium mediated allylation and propargylation reactions of dimethyl acetals and ketals

Indium mediated allylation and propargylation reactions of acetals and ketals with various allyl or propargyl bromides in aqueous media successfully provided the corresponding homoallylic or homopropargylic (and allenylic) alcohol, respectively, in moderate to good yields. Highly chemoselective allylation is also described. The ketal and aryl acetal could be selectively allylated over the aliphatic one in 80-84% yields.

Preparation of Chiral β-Functionalized Allylboronate Reagents and their Application to Asymmetric Synthesis of α-methylene-γ-lactams and and γ-lactones

Various chiral β-functionalized allylboronates are prepared by alkylation of α-functional vinylaluminium reagents with chiral α-chloromethylboronates with excellent yields and high regioselectivity.The ability of these new chiral allylboronates to afford the expected α-methylene-γ-lactams and γ-lactones on treatment with imines and aldehydes is also reported. - Keywords: chiral chloromethylboronate; vicinal diol; chiral β-functionalized allylboronate; α-methylene-γ-lactam; α-methylene-γ-lactone.

Metal-mediated reactions of α-bromomethyl-propenoate esters

Methyl 2-bromomethylprop-2-enoate reacts with benzaldehyde and with salicylaldehyde via its Sn and Zn complexes under aqueous conditions to form α-methylene-γ-lactones in high yields. In the case of salicylaldehyde X-ray analysis proves conclusively formation of a five- rather than a seven-membered ring. Under the above conditions 2-bromomethyl-3-phenylprop-2-enoate does not afford any cyclic products.

Preparation of (2-methoxycarbonyl)allylboronates from (α-methoxycarbonyl)vinylalanate

The first successful preparation of (2-methoxycarbonyl)allylboronates from (α-methoxycarbonyl)vinylalanate and halogenomethylboronate derivatives is described.

ORGANOMETALLIC REACTIONS IN AQUEOUS MEDIA WITH INDIUM

Allylation reactions of aldehydes and ketones occurred smoothly with indium metal in aqueous media.Compared to similar reactions with zinc and tin, the reaction with indium proceeds without the need of any promoter.The reaction can be extended to the synthesis of 2-methylene-γ-lactone 6 via the condensation of carbonyl compounds with 2-bromomethylacrylate 4.