orgo chapter 16 reactions

formaldehyde + gringard + H3O

primary alcohol

aldehyde + gringard + H3O

secondary alcohol

ketone + gringard + H3O

tertiary alcohol

co2 + gringard + H3O

carboxylic acid

ester + 2 gringard + H3O

teritary alcohol (from ester)

primary alcohol (from R'O-)

acyl chloride + 2 gringard + H3O

teritary alcohol

acyl chloride + GILMAN

ketone

carbonyl + acetylide ion + pyridine

alcohol attached to acetylide ion

(acetylide must be deprotonated first to ion using NaNH2)

aldehyde + excess cyanide + HCl

alcohol attached to CN

ketone + excess cyanide + HCl

alcohol attached to CN

alcohol attached to CN + raney nickel + H2

primary amine (CN replaced by CH2NH2)

OH on beta carbon

aldehyde + NaBH4 + H3O

primary alcohol

ketone + NaBH4 + H3O

secondary alcohol

acyl chloride + 2 NaBH4 + H3O

primary alcohol

acyl chloride + LiAl[OC(CH3)3)]3H, -78, H2O

aldehyde

ester + 2 LiAlH4 (2 LAH) + H3O

2 primary alcohols (1 from ester 1 from R'O-)

ester + DIBALH + H3O

aldehyde

carboxylic acid + LAH + H3O

primary alcohol

amide + LAH + H2O

amine

C=N + NaBH4 + H2O

amine

C≡N + NaBH4 + H2O

amine

C=C + H2 Pd/C

alkane

C≡C + 2H2 Pd/C

alkane

C≡C Na or Li + NH3 (liq)

trans alkene

CH=NCH3 + H2 Pd/C

amine

RC≡N + H2 + Raney Nickel

amine

aldehyde + H2 + Raney Nickel

primary alcohol

ketone + H2 + Raney Nickel

secondary alcohol

ketone/aldehyde + primary amine + trace acid

imine (C=N) + H2O

reversible

ketone/aldehyde + secondary amine + trace acid

enamine (C=CN) + H2O
reversible

imine (C=NH) + H2 + Pd/C

primary amine

removes double bond

imine (C=N) + NaBH3CN

secondary amine

removes double bond

enamine + NaBH3CN

tertiary amine

aldehyde/ketone + water + HCl

hydrate (unstable)
reversible

aldehyde/ketone + excess alcohol + HCl

hemiacetal --> acetal + water
reversible

Wolff- Kishner Reaction
Ketone + Hydrazine (H2NNH2) + Base

alkane + N2 gas + H2O

aldehyde/ketone + diol + HCl

cyclic acetal + H2O
protecting group
reversible

alcohol + TMS-Cl + imidazole

silyl ether (R-OTMS)
protects alcohol

silyl ether (R-OTMS) + TBAF or H3O+

alcohol regeneration

carboxylic acid + excess alcohol + HCl

ester + h20 (reversible)
protects OH on carboxylic acid

ketone/aldehyde + thiol (R’SH) + HCl

thioacteal + H2O (reversible)

thioacetal + H2O + H2/Raney Nickel

alkane

Wittig Rxn - forming ylide
PPh3 + Alkyl halide + nBuLi (strong base)

phosphonium ylide (Ph3P=CHR)

Ketone/aldehyde + phosphonium ylide

alkene (groups interchanged) + triphenylphosphine oxide (Ph3P=O)

alpha beta unsat carbonyl
Direct Addition

adding to C=O → alcohol
Kinetic

direct addition conditions

strong bases/gringard w reactive carbonyls
non-bulky carbonyl + strong base
beta carbon sterically hindered

alpha beta unsat carbonyl
conjugate Addition

adding to beta carbon, retain c=o
Thermodynamic

conjugate addition conditions

weak bases (amines, alcohols, water)
strong bases with less reactive carbonyl
gringard + bulky carbonyl
gilman