72676-31-4

Upstream product

• 1885-38-7 cinnamic nitrile 
• 24840-05-9 (Z)-cinnamonitrile 
• 37854-15-2 2-bromo-3-phenyl-2-propenenitrile 
• 2537-48-6 diethyl 1-cyanomethylphosphonate 
• 100-52-7 benzaldehyde 

Relevant academic research and scientific papers

Selective α-Deuteration of Cinnamonitriles using D2O as Deuterium Source

The selective α-deuteration of α,β-unsaturated nitriles using the strong base tBuOK or a metal-ligand cooperative Ru pincer catalyst is described. With D2O as deuterium source and glyme as solvent at 70 °C, tBuOK is an efficient catalyst for deuteration at the α-C(sp2) position of cinnamonitriles, providing access to a broad range of deuterated derivatives in good to excellent yields and with very high levels of deuterium incorporation. While the tBuOK-catalysed protocol does not tolerate base-sensitive functional groups, cinnamonitrile derivatives containing a benzylic bromide or ester moiety were deuterated in excellent yields using Milstein's ruthenium PNN pincer catalyst. Moreover, the activity for H/D exchange of the metal-ligand cooperative Ru catalyst is found to be significantly higher than that of tBuOK, allowing reactions to proceed well even at room temperature. A mechanistic proposal is put forward that involves deprotonation of the cinnamonitrile α-CH position when using tBuOK as catalyst, whereas H/D exchange catalysis with the Ru PNN pincer likely proceeds via (reversible) oxa-Michael addition of D2O. (Figure presented.).

Visible light-mediated metal-free double bond deuteration of substituted phenylalkenes

Various bromophenylalkenes were reductively photodebrominated by using 1,3-dimethyl-2-phenyl-1H-benzo-[d]imidazoline (DMBI) and 9,10-dicyanoanthracene. With deuterated DMBI analogs (the most effective was DMBI-d11), satisfactory to excellent isotopic yields were obtained. DMBI-d11 could also be regenerated from the reaction mixtures with a recovery rate of up to 50%. The combination of the photodebromination reaction with conventional methods for bromoalkene synthesis enables sequential monodeuteration of a double bond without the necessity of a metal catalyst. This journal is

THE WITTIG-HORNER REACTION IN HETEROGENEOUS MEDIA1-X: SYNTHESIS OF α DEUTERATED FUNCTIONAL OLEFINS USING POTASSIUM CARBONATE WITH DEUTERIUM OXIDE.

α-Labelled functional olefins ( percent D >95 percent) are prepared in high yields by the WITTIG-HORNER reaction in the presence of a 6M K2CO3- deuterium oxide solution at room temperature.

Dilithiation of α,β-Disubstituted Activated Olefins: α,β-Dilithiocinnamonitrile

cis- and trans-cinnamonitrile were treated with an excess of LDA in an aprotic medium to give a high yield of one preferred isomer of PhC(Li)=C(CN)Li (C.N.-2Li).The chemistry and stereochemistry of its reactions with various electrophiles (MeOD, MeI, IBuI, RCHO, MeSSMe) was studied and discussed. α-Substituted and α,β-disubstituted derivatives of cis- and trans-cinnamonitrile were obtained.The reaction with MeOD resulted exclusively in a quantitative yield of trans-PhCD=CDCN.It is suggested that substitution at Cα takes place first to yield an equilibrium mixture of the corresponding β-lithiated intermediates: cis-PhC(Li)=C(E)CN and trans-PhC(Li)=C(CN)E.The type and structure of the products obtained in the reaction of this equilibrium mixture with electrophiles depends on factors affecting the nucleophilic reactivity and configurational stability of the Cβ-Li bond of each of these two β-lithiated cinnamonitrile derivatives.

VINYL CARBANIONS DERIVED FROM CIS-CINNAMONITRILE-REACTIONS WITH ELECTROPHILES AND CONFIGURATIONAL STABILITY

Vinyl carbanions derived from cis-cinnamonitrile 1 were formed by reacting it with lithium-diisopropylamide (LDA) as a base in aprotic solvents at low temperatures; reaction with various electrophiles (E) resulted in the corresponding derivatives PhCH=C(E)CN.The configurational stability of the vinyl carbanions derived from 1 and the geometry of the reaction products was effected by the solvating properties of the medium.Retention of configuration was achieved in a poor solvating medium-diethyl ether-hexane (4:1).Addition of a crown ether or using THF as a solvent resulted in products having trans geometry.The site of deprotonation of cinnamonitrile (cis and trans) was compared to that of cinnamic esters and discussed.Determination of the geometry of the products was based on their 1H NMR spectra.