21 - Organometallic

21 - Organometallic - Addition of Organometallic Reagents...

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Unformatted text preview: Addition of Organometallic Reagents to Carbonyls organometallic reagents: a carbon is bound to a more electropositive metal, resulting in a polar covalent bond with substantial negative charge on carbon . these reagents are nucleophilic carbon sources M 3 Ll: M3 ffim‘lfi Mluzlll‘l’lnim —l——> l—l _ (8:983 ENLE = l-O \m’l’k (ea cal: 0112 Poland M0115 Cur Lo h W ‘l’lkln h 0 ”l: "hr-ELM QJ —l_9 _ gal/Lila; ’l‘u MQ9H® McSB“_ (n+3 ENMS - L?) 89 ‘L I\ also known as o~ 67:3,“;er (“304’ I M‘l’k3\ magmas im lorom'oLe’ no Wigwam: : 5 @09le (Wlwt IMO/Q. declvoufla’fim attllmls r,""“\\\\.MMO we low ln Gal—M55 Ll ‘\.\ 25 47: \\ “baud/J '\ X M Ml \ (:4, 4.4—4 ,' 4-595 C orl-lluls \ \ i“ ,’ HOMO ”RU orL-l'lll l5 dole; {A I 0WD / W33 *7? ‘l'luz. CSVX OILlltl§( l‘l’ lS M—o/Q like Q 3.?3 flow QNbum \me PM; How to Make Organometallic Reagents Grignard reagents: ”Tm“ .L was " game“ c N RY‘ Organolithiums: Liwim 04°} “a - l; + LP Q1 Organometallic Reagents are Strong Bases organometallic reagents will react with H20 and other acidic protons consider methyl lithium: _ \ lL 21 lifll lg ‘9 $9 88 +0 l‘k—e fight... walkout) ocmlL ‘l’WMO‘AmMmllB wt vwdale Garb v Que H—orl3 + “20% Yb,” 7 lS.8 FLQ' :: ‘16 41;: Jxe‘)ro‘lbm’\\ovx Cs [email protected] is MKGL +00 walr. ac Lisa lb MW 0. W Q'l‘l- ./\/\L; + ®—E—H ’———9 /\/\@ + ME” 00 w ”h: “*BKL; YE'O» 0‘ C3 +: an Comm Last 4: Si Wm M 25— lko' (3 alkyllil’laim ll’l’h‘tm (Ulla Fmpls wide, (Lh'lbbm SW3 Lu Auk + /\/\Ll /L'i’/L + m G?) h ‘ Ll l’l‘ * SI rm: k g H “WW : ‘0‘” = we remember: a base can deprotonate acids with pKa values that are lower than it’s conjugate acid. \A CAM “~93 EuNLp'z-SEN 1 : [hmmzlllllflwl ‘ [N1 = him??? . l “l“ [mcvq—gEAAL-a [Huang ENHBCW’J ‘ L1 5M Organometallic Reagents are Strong Bases In terms of PKa and equilibrium constants: l: )\b* + /\/\L{ ~L> *T/k 1— /\/\® H U 19ch :3? TL‘ 2 3' kt: _ EL PUP!) N] : ELNIPr,]CH3O:] [N1 [a mall [W1 [H “”51 W103; 063} l: ': lcmllNCD’p l : ”-3? : ‘0”, fl \ ka/V Wm l remember: a base can deprotonate acids with pKa values that are lower than it’s conjugate acid. Organometallic Reagents Add to Carbonyls remember, carbonyls are electrophilic on carbon: QN‘W “\01-0 .. m'gu3'\-bmih music fl Nu. 0" G) A: Q %‘ (”‘/'c. £200 —————=> \C’F’OQ o «v or ‘ / We) fi—A Nw/i“ T" \Gftapl’ Co€¥bciew+ On w‘oun in +‘NQ. 1* GVbH'UJS Lodk cup. foLaH-L—QA ‘i‘owwolj 0*3‘30’“, Surj'x «um/5r have is famfial Poli’h‘u- Me. ovx W12“ a general mechanism for organometallic addition to carbonyl: —H~e_ R1 5”“? 44:41.: +1“. duh-‘3 NH“ ii— b: . 8v» +k4— new km“ tutu-es Vie LAM va on R! XRZ “P \‘Qjoi‘I-l WS—Q Organometallic Reagents Add to Carbonyls Organometallic reagents are nucleophilic at carbon ° addition of organometallic reagents to carbonyls form C—C bonds (fl HfiHz 0 H6990 CH‘ @O 0H3 ‘ 3 |+ 06’) 5 QA + —’—> OX __,__, g; rate +94%er ‘MJFQVM dfdfl 2.‘J ad cohfl 909! M Qfi 0J2 L641 3 ‘ ad intermediate H lemmas flames... ”HUS WW ‘ ‘ 0L Lofl Swev ‘ka Valwfi Qom Ltd? uleh'hfi 300 Or \w‘ms (youths. fLo‘ H2. : LU. fk“ CH1 = '15 z~> a?” K, 2. E) 3® 0H <0 A “j v- H306) 6: + {“BW'M?’ —? ’—*—-3’ + H20 T 3" «leoLol his is Qaued addehsde + 0r (unmehflic fl 2.0 oJco‘uA m “work-wf'—-- {Jr MN)“, (3 JR; 411 SKM‘Koj moi-(Vial {s Mmd £91wa 1' or3otrO-Aehmc ——-—> 3° «leoLd wa W®-J Qfsvhrmnicj ““2 \n WQ‘A‘LLQ Addition of Organometallics to Esters all carbonyl addition reactions can roughly be divided into two categories: +‘3Pic‘d‘3 "HM? kavl 4 RI QADL ‘21 [\Ovvfl when [1‘ moi R1 CH" fir.“ = '18) axe :5“ lean-«3 @o N“, “’OQ‘H (stow: H8 1 "‘i‘ / l R . R Apt Cop”. @O NIL. TYPE: {1" @idakades Md lee/fine; /l|\ Nu. Kym/m K', R2 =— H or C,“ HM R' 1% “> R'A (8 ”+9”, Will—e u TYPEI O E ill JR Nu. - 2. 2 :3 .. '(br 654-03! acid exhale}, 2 “Mi Sma‘ie smiius amidesf Sowdw 0. (—5 (flu-Mg Q, ) weed“ mo‘éj *3 LG, 0. cod ij R1 : 0R area? a MRI. QQ OH (some h M3) Addition of Organometallics to Esters esters undergo double-addition of organometallics 6) CH3 M3Br . THF G)? c H3 0 Q \ EE/k 0% @ H30 , I mg CH3 H 063 TYPE 31: 3 M339 3 o Z0 p 0 6 @ M g Q“: Mfl‘Br / ‘ Q45 CH»3 Q C ‘ CH3 \ 0w 1: 11m; 1; V CH3 T Br @ocH3 T 9 z “‘43 S & dated” 1:0th ‘lS mere [emvincs 3mm? dukoekmc mm 4% ask/q m Secemi Pk“ HOMe = 16 W(Ho« GQCWS Ymrillh. Jdue same, who (Lewis *0 «QM (LUMHQ Md mkyfl/IMS Why Are Ketones More Electrophilic than Esters? can use resonance structures to rationalize reactivity trend: 9 O o o i i (—h—fi' H $30 /U\ CH3 ‘15 HJQ)\K3 CH3 HXC/\\&>/c3 8849/ ”“336“ JanoJ-es dash“ dwukbLfl (enhance New“ 100‘ Swen an in wad of M05: W64). 15 MIA 0’ \‘CSS VMK‘ Tr-it 0,0330“ [One fk‘hf kldmhbej h ? . t M exit-U. 4 “+0 W Ti): weavioivj l4 \esg aimklhc % HSC —- (4+3 / 0%) ovEH—«ls oC S'im'iiou‘ sire: MAL ASL/31:83 W W L4H» <3ka niJVUSe/w ‘W-‘i fans Mocha M wane SMLB qub TV? trend in carbonyl electrophilicity: we»: ML km mam ’ O O (I? J? > RiNRI VH> «U». > Mme > 12 we L (LMM Ee‘m‘e ma clJu’icLQ 24W Mote ...
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