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Mechanistic details
electrophilic addition carbocation intermediates Markovnikov's rule apply carbocation rearrangements possible no relative stereochemical preference
Reaction 2. Radical addition of hydrogen bromide (HBr) to alkenes. (NOT COVERED THIS TIME)
Mechanistic details
Mechanistic details
Mechanistic details
electrophilic addition of X2 bromonium or chloronium ion intercepted by H2O Markovnikov's rule apply (with respect to H2O) anti addition
Mechanistic details
acid catalyst needed with non-nucleophilic counter ion (H2SO4, HClO4, H3PO4) high temperature required often reversible (rather used to make alkenes from alcohols)
electrophilic addition carbocations intermediates Markovnikov's rule applies no relative stereochemical preference
Mechanistic details
Hg(OAc)2 in H2O (or THF/H2O) reduction step required to replace mercury with hydrogen (NaBH4) room temperature
electrophilic addition of mercury compound mercurinium ion as the intermediate intercepted by H2O Markovnikov's rule applies with respect to H2O reduction step with a complicated mechanism the addition of H2O is anti, but reduction scrambles the stereochemistry (i.e. no relative stereochemical preference is observed)
Mechanistic details
BH3-THF complex in THF tri-fold addition (to borane) is common, giving trialkylboranes (R3B) oxidation step necessary (H2O2/OH) room temperature or heat
electrophilic addition of BH3 cyclic transition state, putting boron at the least substituted carbon of the double bond syn addition, preserved in the oxidation step (stereospecific replacement of BR2 with OH)) anti-Markovnikov alcohols
Mechanistic details
H2 gas over heterogeneous catalysts (Pd/C, Pt, PtO2) room temperature very facile reaction (many other functional groups remain untouched)
surface reaction syn addition from the less crowded face mechanism is complicated redox reaction
Mechanistic details
KMnO4/ OH (lower yield) OsO4/pyridine (higher yield but toxic and expensive) catalytic OsO4 with NMO
cyclic transition state and intermediate resulting in syn addition redox reaction
Mechanistic details
Mechanistic details
Mechanistic details
redox reaction oxygen inserts into all former vinylic C-H bonds
Mechanistic details
first addition usually trans second addition often follows less reactive than alkenes
Mechanistic details
electrophilic addition Markovnikov's rule apply first addition usually trans (anti) as if the halonium ion was an intermediate (but most likely it is not) second addition often follows less reactive than alkenes
Mechanistic details
electrophilic addition catalyzed by Hg2+ (mercurinium ion not involved) Markovnikov's rule apply the primary product is an enol, a less stable tautomer of a ketone
Mechanistic details
BH3/THF gives mixture of regioisomers for disubstituted alkynes, double addition with terminal alkynes R'2BH (R' = 1,2-dimethylpropyl) may be used for monoaddition to terminal alkynes
Mechanistic details
Lindlar catalyst used for cis product (Pd, CaCO3, Pb(OAc)2, quinoline) lithium metal in ammonia for trans product
hydrogenation is a heterogeneous reaction hydrogenation catalyst is poisoned (deactivated) to prevent further reduction of the double bond Li reduction involves electron - transfer process and proceeds via an intermediate vinylic carbanion
Mechanistic details
the increased acidity of the sp hybridized carbon makes carbanion accessible (the lone electron pair in the
LDA in THF used as a base primary electrophiles (alkylating agents) work well
conjugate base, acetylide anion, has large s character) SN2 substitution mechanism followed (back-side attack on the electrophilic carbon)
Mechanistic details
complicated oxidation mechanisms more difficult to oxidize than alkenes substituted "ends" yield the corresponding carboxylic acids, unsubstituted ones give CO2
Mechanistic details
HCl or HBr in ether
electrophilic addition leading to allyl (resonance stabilized) carbocations the allyl cation can be attacked by the bromide anion at two positions the 1,2-adduct (A) is kinetically favored (predominates at low temperatures) the 1,4-adduct (B) is thermodynamically more stable and it predominates at higher temperatures
Mechanistic details
Br2 or Cl2 in CCl4 or CH2Cl2
electrophilic addition leading to halonium ion intermediate the 1,2-adduct is kinetically favored (predominates at low temperatures) the 1,4-adduct is thermodynamically more stable and predominates at higher temperatures
Mechanistic details
X2; the reaction is explosive for F2 and very sluggish for I2 (thermodynamic reasons) heat or light used to generate radicals in the initiation steps mixtures of products are obtained (mono- and polyhalogenated compounds, and different regioisomers) NBS in CCl4 (with light or initiators) used for allylic or benzylic brominations
radical chain reactions the initiation step generates X radical selectivity is established in the hydrogen-abstraction step by X the more reactive X, the less selective it is
Mechanistic details
HX in ether (works best for tertiary alcohols) PBr3 in ether or CH2Cl2 SOCl2 in pyridine TosCl/pyridine followed by X
SN1 mechanism for tertiary alcohols SN2 mechanism for primary alcohols hydroxyl group is converted to a better leaving group by reaction with the reagent of choice
Mechanistic details
variety of conditions and solvents usually polar and protic solvents for SN1 reactions usually polar aprotic solvents for SN2 reactions
SN1 mechanism for tertiary substrates: the leaving group departs in a unimolecular rate-limiting step, generating the carbocation, which in the second step reacts with the nucleophile; ion pairs may be involved and carbocation rearrangements may compete SN2 mechanism for primary substrates: the nucleophile displaces the leaving group in one-step bimolecular back-side attack leading to inversion of configuration on stereogenic centers secondary, allylic or benzylic substrates may react by both mechanisms competition with elimination reactions (E1 and E2) often observed
Mechanistic details
variety of conditions and solvents usually strong bases favor E2 mechanism
E1 mechanism for tertiary or secondary allylic or benzylic substrates: the leaving group departs in a unimolecular ratelimiting step, generating the carbocation, which in the second step is deprotonated (with base) on the carbon adjacent to the cationc center, yielding the olefin; carbocation rearrangements may compete E2 mechanism favored by strong bases: the base removes a proton from the carbon adjacent to one bearing the leaving group in a one-step bimolecular reaction that requires periplanar orientation of the hydrogen and the leaving group (antiperiplanar preferred)
competition with substitution reactions (SN1and SN2) often observed Usually the most substituted olefin is the major product (Zaitsev's rule)
Mechanistic details
Br2 and FeBr3 (or AlBr3) for bromination Cl2 and FeCl3 (or AlCl3) for chlorination I2 and H2O2 (or CuCl2) for iodination HNO3/H2SO4 for nitration SO3/H2SO4 for sulfonation RX and AlCl3 for alkylation RCOX and AlCl3 for acylation
positively charged electrophile adds to the aromatic ring in the rate-limiting step; the resulting carbocation reverts to aromaticity by the loss of proton the relative reactivity and regiochemistry of the reaction on substituted benzene derivatives is governed by the nature of the substituent: the substituents that are electron withdrawing by inductive and resonance effects are deactivating and meta-directing; the substituents that are electron withdrawing by inductive effects and electron donating by resonance are ortho- and para-directing and depending on the electron-density balance are deactivating (halides) or activating (O in ethers, N in amines or amides); the substituents that are electron donating by inductive and resonance (hyperconjugation) effects are activating and ortho- and para-directing
Mechanistic details
KMnO4 or Na2Cr2O7
Mechanistic details
Mechanistic details
NaBH4 (or LiAlH4) for aldehydes and ketones LiAlH4 for carboxylic acids and esters BH3-THF for carboxylic acids
the hydrides deliver H to the carbonyl-group carbon (nucleophilic addition to C-O double bond) for carboxylic acids and their derivatives, the tetrahedral intermediate formed loses R'O group, and the newly formed carbonyl group is reduced again
Mechanistic details
nucleophilic addition of electron-rich (carbanion-like) carbon from the organometallic reagent to the
metallic magnesium in ether solvents usually carried out in ether solvents (ether, THF) organolithium compounds (RLi) can be used instead of Grignard reagents
electrophilic carbon of the carbonyl group the addition to esters takes place twice; the initially formed tetrahedral intermediate expels RO, regenerating the carbonyl group which reacts with the second molecule of the organometallic reagent
Mechanistic details
acid with a non-nucleophilic counterion (H2SO4) for tertiary substrates POCl3/pyridine for 2o and 1o alcohols
E1 mechanism for tertiary alcohols E2 mechanism for POCl3/pyridine (POCl3 converts -OH into a good leaving group: -OPOCl2) usually Zaitsev's rule followed (see Reaction 25)
Mechanistic details
PCC (pyridinium chlorochromate) or periodinane for oxidation of 1o alcohols to aldehydes (2o alcohols are oxidized to ketones) Jones' reagent (CrO3/H2SO4/H2O/acetone) or dichromate (Na2Cr2O7) for oxidation of 1o alcohols to carboxylic acids and 2o alcohols to ketones
Mechanistic details
alkoxides are prepared by reaction of alcohols with bases or alkali metals reaction of alkoxides with primary alkyl halides intramolecular reaction yields cyclic ethers
Mechanistic details
HI or HBr for 1o and 2o ethers HI, HBr and HCl for 3o ethers
SN2 for primary ethers (after protonation on oxygen, attack by X on the least substituted of the two carbons) SN1 for tertiary, benzylic or allylic ethers (after protonation on oxygen)
Mechanistic details
direct oxygen transfer from the peroxyacid to the alkene (syn stereochemistry)
Mechanistic details
acid catalysis (H2O, Cl, Br, I as nucleophiles) direct nucleophile addition (HO, RO, RNH2, R2N, RMgX)
under acid catalyzed conditions the protonated epoxide can be attacked by the nucleophile at the more (usually the major site of attack), or the less substituted site, depending on substitution patterns (anti stereochemistry results) direct nucleophilic attack (SN2) takes place at the least