Aromatic nitro compounds are readily reduced by $\ce{SnCl2.2H2O}$ in alcohol or ethyl acetate or by anhydrous $\ce{SnCl2}$ in alcohol where other reducible or acid sensitive groups such as aldehyde, ketone, ester, cyano, halogen, and O-benzyl remain unaffected. The isoxazoline derivatives are further converted into β-hydroxy ketones or β-amino alcohols. [21], CS1 maint: multiple names: authors list (. However, the protocol is not applicable to nitromethane. Beta-Nitro Alcohol. described this process as the organocatalyst functioning as Lewis acid or base or Brønsted acid or base. [2][4] The Henry reaction is a useful technique in the area of organic chemistry due to the synthetic utility of its corresponding products, as they can be easily converted to other useful synthetic intermediates. The reduction of polynitroaromatic compounds is complicated by multi-step processes. [16], A diastereoselective variation of this reaction is depicted below. This type of reaction is also referred to as a nitroaldol reaction (nitroalkane, aldehyde, and alcohol). Lin, in Comprehensive Heterocyclic Chemistry, 1984. Iron (III) Chloride Test for Water-Soluble Phenols. H. Sasai, in Comprehensive Organic Synthesis II (Second Edition), 2014. Reason : : There is a repulsion between the two bulky (—R) groups. However, the treatment of α-nitroketone tosylhydrazones with DBU eliminates nitrous acid, affording enone tosylhydrazones exclusively as (E)-isomers (Scheme 71) <1995T4173 >. Sodium borohydride is also a much less hazardous reagent than lithium aluminum hydride. in the total synthesis of the complex alkaloid natural products (−)-nakadomarin (62) and (+)-manzamine A (65)88,89 (Scheme 23). Obviously, the nucleophilicity of this reagent is a drawback of the method.98 More recently, Carreira et al. [3] In recent years, research focus has shifted toward modifications of the Henry reaction to overcome this synthetic challenge. Learn how and when to remove this template message, "Organocatalyzed diastereoselective Henry reaction of enantiopure 4-oxoazetidine-2-carbaldehydes",, Wikipedia articles that are too technical from May 2019, Creative Commons Attribution-ShareAlike License, This page was last edited on 24 September 2020, at 15:10. J. Eustache, ... P. Van de Weghe, in Comprehensive Organic Functional Group Transformations II, 2005. Beta-Nitro Alcohol. Consumer information for this minor interaction is not currently available. D.J. Scheme 23. G.P. We use cookies to help provide and enhance our service and tailor content and ads. It has a role as a xenobiotic metabolite. Because of this property, C−H bonds alpha (adjacent) to the nitro group can be acidic. Di-N-methylated aromatic amines were obtained during the reduction of nitro group in the presence of formaldehyde (Scheme 22) <73OSC(5)552, 76IJC(B)904>. The nitro group is not usually present in targets of biological relevance. The conversion of nitro compounds into carbonyls is known as the Nef Reaction. A 2-amino group in chroman is more labile than its isomers and is hydrolyzed to the alcohol by acids; for example both the amines (699) and (700) give the corresponding alcohols by treatment with nitrous acid and 50% hydrochloric acid, respectively. [12] carbon chain) as well as a transition state that minimizes dipole by orienting the nitro group and carbonyl oxygen anti (on opposite sides) each other. One of the many features of the Henry reaction that makes it synthetically attractive is that it utilizes only a catalytic amount of base to drive the reaction. Detection tags with high vapor pressure, particularly 2,3-dimethyl-2,3-dinitrobutane (DMNB), are commonly added to commercial explosives to facilitate the vapor detection of explosives with relatively low vapor pressure such as plastic explosives. Other examples include the use of tellurium <80AG(E)1008, 80AG(E)1010, 84CL853, 86CL549> and ruthenium complexes <80TL2603, 84BCJ2440>. Copyright © 2020 Elsevier B.V. or its licensors or contributors. [1] Examples. 6-Amino-chromans are of interest because of their chemical and biological resemblance to the tocopherols. The tocopheramines (701; R1, R2, R3 = H or Me) show antioxidant and other properties of the corresponding phenols and are no more toxic. From: Comprehensive Heterocyclic Chemistry, 1984, A.R. Nitro groups on aromatic rings have been reduced to the amine with a variety of common reducing agents and other reagents. Such processes are strongly dependent on the pH, the number of nitro groups per molecule, their relative position on the ring, and the nature and position of other substituents present on the aromatic system [4]. Due to its strong electron-withdrawing nature, a proton at the α-position of the nitro group (pKa is approximately 10) is easily abstracted even by a weak base (Scheme 1). Nitroalkene. Henry reaction and aza-Henry reaction. The first reported primary nitroalkanes in C-allylation with cinnamyl acetate and 2-butenyl acetate catalyzed by Pd(PPh3)4 appeared in 1982.55 Sterically demanding 2-nitropropane gave C-allylation product in only 29% due to the severe competing O-allylation (equation 28).56. The aza-Henry reaction is also used to produce nitroamines and can be a reliable synthetic route for the synthesis of vicinal diamines.[13]. Due to a number of factors, including the reversibility of the reaction, as well as the tendency for easy epimerization of the nitro-substituted carbon atom, the Henry reaction will typically produce a mixture of enantiomers or diastereomers. Langjr., Y.-I. The same catalyst system also worked well for the allylic alkylation of nitroethane with acyclic 1,3-dimethyl allyl substrate, which formed two vicinal chiral centers with good diastereoselectivity and excellent ee (equation 33).63 The reaction was intriguing that lowering the catalyst loading increased both diastereo- and enantio-selectivities. Unfortunately, the scope of the method is restricted to benzylic nitroalkanes as highlighted in Scheme 24.99. 4-nitrobenzyl alcohol is a member of the class of benzyl alcohols that is benzyl alcohol substituted at the para-position by a nitro group. Scheme 2. Through the use of particular derivatives, they were able to induce direct enantioselection through the use of the proper catalyst. The nitro group is also strongly electron-withdrawing. The nitro group is an excellent electron acceptor. Despite this and other related transformations, recent developments in the reductive cleavage of nitroalkanes leading to the formation of the respective alkanes, since the pioneering studies of Ono and co-workers, are limited. Katritzky, J.M. Usually the Henry reaction is an equilibrium reaction, and nitromethane is often used in excess amount to obtain the nitroaldols in satisfactory yield. The nitro group, \(\ce{-NO_2}\), like the carboxylate anion, is a hybrid of two equivalent resonance structures: The hybrid structure has a full positive charge on nitrogen and a half-negative charge on each oxygen.


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