TY - JOUR
T1 - Aza-Henry Reactions of 3,4-Dihydroisoquinoline
AU - Ahamed, Muneer
AU - Thirukkumaran, Thiru
AU - Leung, Wing
AU - Jensen, Paul
AU - Schroers, Jade
AU - Todd, Matthew
PY - 2010/11
Y1 - 2010/11
N2 - The aza-Henry reaction of 3,4-dihydroisoquinoline is reported. The reaction is favourable in excess nitromethane under ambient conditions. Isolation of the unstable reaction product is achieved by acylation or alkylation, allowing the synthesis of Reissert-like compounds in good yields from a one-pot, three-component coupling. The rates of reaction for dihydroisoquinoline and the corresponding benzylisoquinolinium ion have been investigated in the presence and absence of base. The reaction with dihydroisoquinoline probably proceeds via an azinic acid tautomer of nitromethane, a reaction pathway unavailable to the isoquinolinium ion. The traditionally problematic reduction of two of the resulting β-nitroamine derivatives was achieved, providing access to a number of new chiral vicinal diamines. 3,4-Dihydroisoquinoline reacts with nitromethane, likely via a cyclic mechanism employing nitromethane's azinic acid tautomer. The product may be alkylated or acylated. Alternatively a Reissert-like one-pot, three-component coupling may be used to generate a range of β-nitroamines which may be reduced to give new isoquinoline-derived chiral, vicinal diamines.
AB - The aza-Henry reaction of 3,4-dihydroisoquinoline is reported. The reaction is favourable in excess nitromethane under ambient conditions. Isolation of the unstable reaction product is achieved by acylation or alkylation, allowing the synthesis of Reissert-like compounds in good yields from a one-pot, three-component coupling. The rates of reaction for dihydroisoquinoline and the corresponding benzylisoquinolinium ion have been investigated in the presence and absence of base. The reaction with dihydroisoquinoline probably proceeds via an azinic acid tautomer of nitromethane, a reaction pathway unavailable to the isoquinolinium ion. The traditionally problematic reduction of two of the resulting β-nitroamine derivatives was achieved, providing access to a number of new chiral vicinal diamines. 3,4-Dihydroisoquinoline reacts with nitromethane, likely via a cyclic mechanism employing nitromethane's azinic acid tautomer. The product may be alkylated or acylated. Alternatively a Reissert-like one-pot, three-component coupling may be used to generate a range of β-nitroamines which may be reduced to give new isoquinoline-derived chiral, vicinal diamines.
KW - aza-Henry reaction
KW - nitro-Mannich reaction
KW - Nitroalkanes
KW - Nitrogen heterocycles
UR - http://www.scopus.com/inward/record.url?scp=78349276135&partnerID=8YFLogxK
U2 - 10.1002/ejoc.201000955
DO - 10.1002/ejoc.201000955
M3 - Article
VL - 2010
SP - 5980
EP - 5988
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
SN - 1099-0690
IS - 31
ER -