Synthesis of vinyl nitriles

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Allyl-nickel catalysis enables α,β-dehydrogenation of carbonyl compounds. In addition, an oxidative cycloalkenylation reaction provides access to bicycloalkenones with fused, bridged, and spirocyclic ring systems using unactivated ketone and alkene precursors.
D. Huang, S. M. Szewczyk, P. Zhang, T. R. Newhouse, J. Am. Chem. Soc., 2019, 141, 5669-5674.

A simple three-step single-pot procedure for Z-stereoselective synthesis of β-monosubstituted acrylonitriles involves olefination of aldehydes with an in situ generated α-diaminoboryl carbanion species. Various aromatic and aliphatic aldehydes were smoothly converted into the corresponding (Z)-olefin products in good yields.
T. Tomioka, Y. Takahashi, T. G. Vaughan, T. Yanase, Org. Lett., 2010, 12, 2171-2173.

An inexpensive homogeneous iron catalyst enables a direct approach to alkenyl nitriles from allylarenes or alkenes. Three C-H bond cleavages occur under the mild conditions during this process, involving the cleavage of the allyl C(sp³)-H bond as the rate-determining step.
C. Qin, N. Jiao, J. Am. Chem. Soc., 2010, 132, 15893-15895.

A catecholaldimine ligand based nickel(II) complex showed excellent catalytic activity for the conversion of aromatic and heterocyclic alcohols into trans-cinnamonitriles in a one-pot manner via oxidative olefination in the presence of KOH. A direct conversion of alcohols to aldehydes is also reported.
V. Sharma, K. A. Chavan, G. Mali, D. Sarkar, P. Lama, M. Majumder, R. D. Erande, R. K. Metre, J. Org. Chem., 2023, 88, 7448-7453.

A well-defined base transition-metal Co complex catalyzes a switchable α-olefination and α-alkylation of nitriles with primary alcohols. A broad variety of nitriles and primary alcohols are selectively and efficiently converted to the corresponding vinyl nitriles. This environmentally benign and atom efficient transformation produces only H₂ and H₂O as byproducts.
K. Paudel, S. Xu, K. Ding, Org. Lett., 2021, 23, 5028-5032.

An α-olefination of nitriles using primary alcohols, via dehydrogenative coupling of alcohols with nitriles is catalyzed by a manganese pincer complex. The reaction runs in the absence of any additives, base, or hydrogen acceptor, liberating dihydrogen and water as the only byproducts.
S. Chakraborty, U. K. Das, Y. Ben-David, D. Milstein, J. Am. Chem. Soc., 2017, 139, 11710-11713.

An iron(0) catalyst system achieves chemoselectivity between borrowing hydrogen and dehydrogenative coupling protocols by simply changing the base. A broad range of nitriles and alcohols, including benzylic, linear aliphatic, cycloaliphatic, heterocyclic, and allylic alcohols, were selectively and efficiently converted to the corresponding α-alkylation or α-olefination products.
R. R. Putta, S. Chun, S. B. Lee, J. Hong, S. H. Choi, D.-C. Oh, S. Hong, J. Org. Chem., 2022, 87, 16378-16389.

A combination of pyrenedione (PD) and KOtBu achieves a facile alcohol dehydrogenation under visible-light excitation in the presence of aerobic oxygen as the terminal oxidant. The resulting carbonyl compounds can be easily converted to vinyl nitriles in a single-pot reaction. This environmentally benign, organocatalytic α-olefination of nitriles operates at low temperature.
A. K. Bains, Y. Ankit, D. Adhikari, Org. Lett., 2021, 23, 2019-2023.