The non-alternate behavior of the nitro functional group is dramatically illustrated in the transfor ophilic i provided in Scheme VIll. In both instances the derived anions 16 and 17 are highly nucle- mation The non-alternate charge affinity patterns of these nucleophiles is provided Scheme vili Deprotonated Nitronate anions n-BuLi (-)(-) FG→C-C(9) 8°C tion, The nitro group also exhibits the potential of undergoing direct displacement under specific condi- ous literature precedents for this general class of reactions. 14 while table Il provides some of the cl er- tions, a general transformation characteristic of E-functions. a recent review by Tamura provides numer- actions. Although the NO2 group cannot be considered as a general leaving group, there are a number of conditions under which this moiety can be exploited, particularly when it is either allylic or tertiary (10) Table Ill. Representative Substitution Reactions of the Nitro Group(eq 10) NO. Pd(PPh3) CH(CO2Me)2 NaCH(CO2Me) Pd(PPh3)3 Me TiCl SO2 Ph 65% Nao, SPh Pd(PPh3h SPh a particularly useful transformation of the nitro group is the Nef Reaction, a process which trans forms NO2 into=O(Scheme IX). A recent comprehensive review of this transformation provides a detailed discussion of this process. 15 In addition to the Pinnick review, Seebach has also written a comprehensive eview of the diverse chemistry of the nitro functional group. 16 3)(a)Henning, R. Lehr, F; Seebach, D. Helv. Chim. Acta 1976, 59, 2213-2217;(b)Seebach,D,Henning, R.Lehr 14F. Gonnerman Tetrahedron lett. 1977,11610064 15) Pinnick,H Reactions1990,38,655-792 16) Seebach, D. Ce F Weller. T: Chimia 1979.33.1-18Functional Group Classification page 7 The non-alternate behavior of the nitro functional group is dramatically illustrated in the transfor￾mations provided in Scheme VIII. In both instances the derived anions 16 and 17 are highly nucle￾ophilic.13 The non-alternate charge affinity patterns of these nucleophiles is provided. N O N O O C O C CH3 Li CH2Li CH3 N O O C CH3 H FG C N FG C C O O C CH3 CH3 17 16 Scheme VIII Deprotonated Nitronate Anions (–) (–) (–) (–) n-BuLi -78 °C (9) (8) -78 °C LDA – – + + – – – – + – – + The nitro group also exhibits the potential of undergoing direct displacement under specific condi￾tions, a general transformation characteristic of E-functions. A recent review by Tamura provides numer￾ous literature precedents for this general class of reactions.14 while table III provides some of the cited re￾actions. Although the NO2 group cannot be considered as a general leaving group, there are a number of conditions under which this moiety can be exploited, particularly when it is either allylic or tertiary. N O O CH R R Nu CH R R FG C – + Nu(–) (+) + NO (10) 2 – NO2 N H N(CH2 )5 CH(CO2Me)2 SO2Ph NO Ph 2 Ph Me Me SPh NO2 SiMe3 Me Me Me NO2 t-Bu OMe Me Me SPh Me Ph SPh NO2 Me Ph SPh CN Pd(PPh3)3 NaCH(CO2Me)2 NaO2SPh Pd(PPh3)3 Pd(PPh3)3 SnCl4 74% Anisole 94% SnCl4 TiCl4 65% 73% TiCl4 Me3SiCN Table III. Representative Substitution Reactions of the Nitro Group (eq 10). A particularly useful transformation of the nitro group is the Nef Reaction, a process which trans￾forms NO2 into =O (Scheme IX). A recent comprehensive review of this transformation provides a detailed discussion of this process.15 In addition to the Pinnick review, Seebach has also written a comprehensive review of the diverse chemistry of the nitro functional group.16 13) (a) Henning, R.; Lehr, F.; Seebach, D. Helv. Chim. Acta 1976, 59, 2213-2217; (b) Seebach, D.; Henning, R.; Lehr, F.; Gonnermann J. Tetrahedron Lett. 1977, 1161-1164. 14) Tamura, R.; Kamimura, A.; Ono, N. Synthesis 1991, 423-434. 15) Pinnick, H. W.; Org. Reactions 1990, 38, 655-792. 16) Seebach, D.; Colvin, E. W.; Lehr, F.; Weller, T.; Chimia 1979, 33, 1-18