DIEL’S ALDER REACTION This is a reaction in which conjugated diene react with a substituted alkenes known as dienophile to form an adduct known as cycloalkane. This is an example of cycloaddition reaction in which two unsaturated molecules combine to form a cyclic compound with pie electron being used to form two new B bonds. This reaction is [4 + 2] eyclo addition, since it involves a system of 4 ne" and a system of 2 xe’, The reaction occur spontaneously by the application of heat. C a : — SS Diene + Dienophile ‘The stereochemistry of the diene is very important for'the reaction to occur, it must be in Cis form not trans form a Cis form Trans form ‘The reaction that occurs in this process is concerted reaction. Diel-Alder reaction are reversible which is known as retro diel’s Alder reaction. Reaction of ethane with diene does not proceed readily but substituted alkene reaction is very faster when we have electron deficient atom attached to dienophile Electron deficient atoms are. NH NO ete° 44 he AR 2 Propanal Cyclohexene-4- carboxaldeli ° H oe i c= ‘The product always contains one more ring the reactant. Hse. ; 9 Hae. +4 agp Bee 0 SS ° ° 1 1-1 -3-dir Maleic anhydride 2-methylbutan-1-3-diene — Maleic anhydride I-methyleyclohexan-4-5-dicarboxylic acid 9° cl : cl L x Co ° ° 2-chlorobutan-1-3-diene Yor =OWITTING REACTION The reaction of alkyl halide with triphenyl-phosphine gave an intermediate zwitterion known as ylide. This ylide react with aldehyde and ketones under basic conditions to form an initial intermediate called a Betain. The betain then decomposes to an alkenes and triphenyl-phosphine oxide, this is generally known as the witting reaction. It is of great importance to the synthesis of alkenes. R R ® R. ° Sein: a PPhy Scuren8e SG Ra R Ra r—— ¢ — Rt Ph3 1 of Ph;P =o +RR'C—=—=CR’R’ «——— _ R—C CHR? PhyP ° Betain * Non-stabilise ylide: If R and Rin the original alkylhalide are hydrogen or simply alkyl group, the a-hydrogen of the phosphonium salt is very weakly acidic and a very strong base (usually butyl lithium or phenyl lithium) is required to produce the ylide, the ylide, once formed, is a highly reactive compound and is not generally isolable; it is not only strongly basic (deprotonating acid as weak as water), it is strongly nucleophilic in the manner of a grinardreagent which reacts rapidly under mild conditions to give the betain which then decomposes rapidly and spontaneously to give the alkenes. If stereoisomerism in the product is possible, a mixture of E and Z isomers is generally obtained. @ ° ° © CH;Br —PPhs_, CH;PPh3Br —_NaH_, | cy, PPh; (CH3)20 ‘O CH2 64% PPh: o oneB,> _NaNH; © e cHyBr —PPhs_, CH;PPh3Br_ —"“%_ | CH, PPh; NH Ether CHO CH, CHO cH cH 2hr 35" 75% 2 5 aes & CoH;x —PPhs = c,[Link] BCaHobi — ri or NaNHp | PhCHO PhCH ‘CHCH3 (Z and E) 68 - 98% + The isomerisation ratio depends on the nature of X and the base used where X - HalogensStabilised ylide If Rand R! is an electron withdrawing group e.g, Ester, deprotonation of the phosphonium salt is achieved under much less strongly basic conditions and the resulting ylide is often sufficiently stable to be isolated, it is also sufficiently stable for its addition to carbonium group, to be reversible although it is a relatively weak nucleophile and may not react readily with feebly electrophile carbonium group, where E- and Z- isomers of the final product can exists, itis the E- isomer which normally predominate. PPh; ° oF woo py 3 BrCH,CO,C2H; —PPhs, ph;PCH,CO,C,HsBrH ~NaQHof py.p ——cHco,C,H, NaOCjHs CHs0,CHC WP 43% PRP creo, PhCHO eocs ° cuscH / 20 Several days 2 days ets CH; ==" ©) - PhCH==CHCO,CoHi; a < 7% 89% Z Steric control in the witting reaction In general, witting reactions involving non-stabilise ylides are not highly stereoselective, hence a mixture of E- and Z- alkenes are usually obtained. Modified procedure however make it possible to obtain predominantly one of the two isomers. Ifa non-stabilise ylide can be obtained in a solution free from inorganic salts (¢.g. By using sodalime as the base and filtering off the sodium halide), it’s reaction with an aldehyde gives predominantly Z- alkene.