Diene nucleophilic addition

The HX compounds are electrophilic reagents, and many polyhalo and polycyano alkenes, (e.g., Cl2C=CHCl) do not react with them at all in the absence of free-radical conditions. When such reactions do occur, however, they take place by a nucleophilic addition mechanism, (i.e., initial attack is by X ). This type of mechanism also occurs with Michael-type substrates C=C—Z, where the orientation is always such that the halogen goes to the carbon that does not bear the Z, so the product is of the form X—C—CH—Z, even in the presence of free-radical initiators. Hydrogen iodide adds 1,4 to conjugated dienes in the gas phase by a pericyclic mechanism ... 

The possible reaction pathways for the stereoselective E- and Z-allylation are illustrated in Scheme 7. 1-Silyl-l,3-dienes 22 react with a Ni-H species in the presence of PPI13 to provide a syn-it-allylnickel species 24, the least substituted allylnickel species, which undergoes nucleophilic addition to an aldehyde at the least substituted allylic terminus to provide ( )-allylsilanc ( )-23. It should be noted that the regioselectivities observed for the Ni-H addition to a diene 22 and nucleophilic addition of 24 to aldehydes are opposite to those observed so far in many precedents in this review (e.g., Eqs. 4 and 6). 

Nucleophilic additions to carbonyl groups lead to alcohols which on dehydration, furnish alkenes70,71. This two-step protocol has been extremely useful for diene and polyene synthesis with wide variation in the carbonyl substrate and the nucleophilic addendum. Diene synthesis using aldol-type condensation as well as phenyl sulphonyl carbanion (the Julia reaction) are also discussed in this section. 

As mentioned above nonconjugated dienes give stable complexes where the two double bonds can form a chelate complex. A common pathway in palladium-catalyzed oxidation of nonconjugated dienes is that, after a first nucleophilic addition to one of the double bonds, the second double bond inserts into the palladium-carbon bond. The new (cr-alkyl)palladium complex produced can then undergo a /(-elimination or an oxidative cleavage reaction (Scheme 2). An early example of this type of reaction, although not catalytic, was reported by Tsuji and Takahashi (equation 2)12. 

Subsequently, Corey and coworkers40 42 described nucleophilic addition reactions of organocopper reagents and organocuprates to several acceptor-substituted dienes. The... 

Nucleophilic additions of amines to acceptor-substituted dienes were examined as early as 1950. Frankel and coworkers98 found that the reaction of 2,4-pentadienenitrile with various secondary amines proceeded regioselectively to furnish the 1,6-addition products (equation 29). In some cases, these could converted into the 2,4-diamino-substituted pen-tanenitriles by isomerization and 1,4-addition of a second molecule of amine. Analogous results were reported by other groups17,99 100 and extended to hydrazine as nucleophile101 and to vinylcyclobutenones48 and dienoates102-104 as Michael acceptors. 

Only few examples have been reported so far on nucleophilic addition reactions to acceptor-substituted polyenes123,124,186 188. In 1933, Farmer and Martin186 examined the reaction of methyl 2,4,6-octatrienoate with sodium dimethyl malonate and isolated the 1,4-adduct as major product (equation 81). In contrast to this, 3,5,7-nonatrien-2-one and ethyl 2,4,6-octatrienoate react with organocuprates under 1,8-addition to provide the 4,6-dien-2-ones and 3,5-dienoates, respectively (equation 82)187. 

Cyclopentadiene(diene)cobalt complexes, the largest catagory of diene complexes of Co, may be prepared by direct complexation, by preparation of the dienes within the coordination sphere of Co and by nucleophilic addition to ( j5-dienyl)CoCp cations. In comparison to (diene)CoCp complexes, there are considerably fewer examples of (diene)RhCp and (diene)IrCp complexes known. 

Examination of the reactivity of acyclic (diene)Fe(CO)3 complexes indicates that this nucleophilic addition is reversible. The reaction of (C4H6)Fe(CO)3 with strong carbon nucleophiles, followed by protonation, gives olefinic products 195 and 196 (Scheme 49)187. The ratio of 195 and 196 depends upon the reaction temperature and time. Thus, for short reaction time and low temperature (0.5 h, —78 °C) the product from attack at C2 (i.e. 195) predominates while at higher temperature and longer reaction time (2 h, 0 °C) the product from attack at Cl (i.e. 196) predominates. This selectivity is rationalized by kinetically controlled attack at the more electron-poor carbon (C2) at low temperature. Nucleophilic attack is reversible and, under conditions where an equilibrium is established, the thermodynamically more stable (allyl)Fe(CO)3" is favored. The regioselectivity for nucleophilic attack on substituted (diene)Fe(CO)3 complexes has been reported187. The... 

Nucleophilic addition to acyclic (diene)Mo+ cations has been examined. For (isoprene) Mo(CO)2L (L = Cp, Cp, In), the regioselectivity for nucleophilic attack has been found to depend on the nature of the nucleophile, the ligand L, the reaction solvent and the temperature21,813 833 193. The generation and in situ reactivity of transoid acyclic (diene)molybdenum and tungsten cations with nucleophiles has been previously mentioned (Section IV.C.2). 

Nucleophilic additions to (cyclohexadienone)Fe(CO)3 complexes (218) occur in a dia-stereospecific fashion (Scheme 56)197. For example, the Reformatsky reaction of ketone (218a) affords a simple diasteromeric alcohol product19715. The reduction of (1-carbo-methoxycyclohexa-l,3-dien-5-one)Fe(CO)3 (218b) to give 219 has been utilized in the enantioselective synthesis of methyl shikimate. In a similar fashion, cycloadditions of (2-methoxy-5-methylenecyclohexa-l,3-diene)Fe(CO)3 (220) occur in a diastereospecific fashion198. 

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