PERicyeLi¢ REACTIONS * Pevieyetie yeactions ane concerted. (Do NOT involve intermediats) x i conj Syste ‘ accur in conjugated systems “nin se E B |Categories|; (i) Electrocyelizakions roca Pad (ii) cyelo- addition yeackions Te (iil) Sigmartropic rearmauyements Nate @ Molewton Orbital Diagrawn> Yn > Wem no. of Nodex =(n-1) Example 4: ——— inet Hg = CHa Y, LUMO — 4, HOMO HO Reale. E Cine. ions =e %—¥ y, Homo AE yy + ( tere neds) o config > Ye config > 4 Ye Example 2: fees ne i= IT ae i ee C3 nda) Hf Kelee. =4 i = , Ankbon t= EM hy 3 eae rae Ca nedaty — st Gondin g yy y, Ae Homa Y, 4 Orbital Give yo hy a + "4 (-teranads) a ’ config > ye ye Ys Y4 cog > YMAElectrowyelizalions WU Frontier Molecular Orbit Theory (FMQ): eaanher Ea ee aay Ds HOMO Of the veackng partner will ditemine Row the ey dizakon (or reversion) occwis | @ 4K System we nte ——+ Remember + far (He Syston H H * % je ie e ae oes Ye (HOH) 4. | (HoMe)¥, Ae w+ % + Yi te ee Thermal : Energy (A) Photo chamal cal Eneeyy (Rv) HOMO 4, Cunexcited stake) BO Me Mée n W cg & CONAOTATION] For bendicg 2 G ® DISRITATION {for bonding Me Homo 3 C Excited stare) Me@ 6h System: Remembev: 6 Ke System ~ — Ww SZ, |= aha %4 — Yq 5 (HOMO) we YH Me (Homo) Ys. He &, = Gone Ys 4 Ys 4b Mo ae Mi 4e (usexcited ) CExcikd) wma [eit “ot a @ HOMO —> Ys, HomMo—> V4 ‘oh DIS ROTATION nt 7 CONROTATION , wh Qn QQ, 3 Me a) 1 tm =m e MK RULES OF ELECTROCYCLIZATION : RARE ose pias eee Thermal Photachemiak (4) (4) 4m% > CON Dis 6H — dis CONSome _Examplys Elechoey clizakion O 8 u HS G- A n?. 8 ——+ ees =<" Disrotakion i H 6 he syste! (100%) " a iH a Conretaken "OME Ene Cytun! aa 1 Ke System! | Risrotalion W he 4 a g 6 need ° con f “Me Stable!4 eeu) Aga Tins FMO Theory: HoMo aud LUMO cf the reactants shewld, howe complementary phases fer bonding es era Ue “1 i@ = Tan * 4m) J fey [col l L oo CO H Case 4: (ah + 2m) cycloaddition. => wh oo 1 (unexcited) (excited) undsr thermal condilon undur pholochemical condi Hon va y fv 4 Homo s- 4% Phase D Favorable banding | r 2 pigmalely ¥ yy LuMo = CSame phase) 2 J Phase Marching | No Reackion | Reackon occurs! % Rule: ant 2K —p* Thermally —> NOT Allowed! + Photochwuicaty —> Allowed |fe Cane 2: 4R+20 cycloaddition . I \) ey lai de ot 3 f Foworable banding inkeracon | = ex) iY ¥, (Lum) Phase Marching) ih Thermaly anwed, Rule: "4h syskm: (K+ aR) + A> XK GR sysem: (AR +2R) > A> ~~ BB Diels—Aldar cycloaddition Reackon ; coe na AO maa Gin 4. (3 (Dieney (Dienophile) * Examples: one Gi) Regioselectivity ° OMe 0 0 A One ‘ eC me et oni Regio tcomens Yr & one One one Fe =\ 7 i CHinor) f 0(ti) StereocRemistry of Diene & Dienophile ove maintained. Me e w ft [ ot Cl +t ++ 2 Fu He ° ve 9 fe He its ® 2 — 2 D at i “ON we ve (ii) Conformakanal Effect. fork Yu“ Preeold, cisgoid, assoid spransoid, i. (transoid |) 0 ° ®) 2rMe © meme > (ORK i xX (trangoid) Steric hindrawe “ (cisseid) (iv) SubsHtuent Effect . o c of pune 4 cm o 1400 ‘ | i we He oF Me 300 He (Elet: Rich Diene) Elec. releasing groups decreases the thermal oxkvation baru |(Y) eyetic: Struckous. & + rhe +e Endo brodudr (Major) Secondary Orbikah interaction! (Alder's Endo selec kvity i ° EASs, —_ cht Exo bro 7 a H i @ Some Examples o y+ ye +t Q oO 7 + Be oo (exes) se Se See €b0.¢ “SCO EE 3 i fm we to aT roe 0, ® o OLS a ie OS ©, sac —=— C0, te oc oeSIQMATROPIC REARRANGEMENTS i 4[%v 22 ne aS F a [1 3-shife] [ B Rules: © cansider te HOMO of the Signa () bond - G) consid the LUMO G the conjugated Aystem. G) In-bhase Combination sf orbitals | example}: A - 13 will NOT mately Me... oe Subra facial xX 3 133 Antonia fadiah ae meal salt | “Weannot hobb Rene! 2h Ye (Buk Phake Matcha) (evo) * example 2 : a supenfacnt un a (153s pntonafaciod ans yet LuMO ' * — eXOmple 3 : pape. 4 Antoafaod if O04@ Rubs Sapmtobls, Reece: Thermal (2) Phatechumicl (r2) 4e/¢e Antone, Suproy 6e/we Supra Antona ee Examples: 6 0,3] " o Ma 7 TOA ce) 3 (2 J3> Me Be ie J Nee Lye (40-1) Hore cubst twad i 7 =" daub bond, | M «5 ; woe? di Me tap cae eee wo Ae ao... Oo m Ff [333 CLAISEN Rearvcangemmnt |