reagents ochem - part 1 (unit 4/5 review)

HX

alkene → haloalkane

alkyne → geminal dihalide

H2O/H2SO4, HgSO4

alkene → alcohol

alkyne → enol → ketone

X2

alkene → vicinal dihalide (anti)

alkyne → tetrahalide (anti)

X2/H2O

alkene → halohydrin (anti)

BH3/THF then H2O2, HO-

R2BH/THF then H2O2, HO-

alkene → alcohol (syn)

alkyne → enol → aldehyde

CHO/H2SO4

alkene → ether

bases for acetylide anions

NaH, NH2-, NaNH2

≡ -

acetylene anion → ≡CH2CH2OH

H2/Pd,Pt, or Ni

alkene → alkane (syn add of H2)

2H2/Pd-C

alkyne → alkane (syn)

H2/Lindlar catalyst

alkyne → cis alkene (syn)

Na/Nh3

alkyne → trans alkene (anti)

LiAlH4/H2O

RX → RH

epoxide → alcohol (opens up)

RCO3H

alkene → epoxide (syn)

RCO3H/H2O (H+ or HO-)

alkene → 1,2-diol (anti)

(1) OsO4, NMO (2) NaHSO3, H2O

or

KMnO4, H2O, HO-

alkene → 1,2-diol (syn)

(1) O3, (2) Zn, H2O, or CH3SCH3

alkene → ketones + aldehydes

(1) O3, (2) H2O

internal alkyne → carboxylic acids

terminal alkyne → carboxylic acid + carbon dioxide

PCC

1° alcohol → aldehyde

2° alcohol → ketone

CrO3/H2SO4, H2O

1° alcohol → carboxylic acid

2° alcohol → ketone

mCPBA

mcPBA then H3O+

alkene → epoxide

alkene → trans-1,2-diol (anti)

NaBH4

ketones and aldehydes → secondary/primary alcohol

KOH/EtOH or NaOEt/EtOH

E2, most substituted alkene

t-BuOK/t-BuOH

bulky (least substituted) alkene E2 elimination

POCL3/pyridine

alcohol → zaitsev alkene (converts OH to good LG)

H2SO4/heat

alcohol → zaitsev + rearrangement alkene

PBr3/ether

1°/2° Alcohol → alkyl bromide

SOCl2/pyridine

alcohol → alkyl chloride

NaOCH3/CH3OH

methyl ether or elimination product

NaOH/H2O

alcohol (from R-X)

H3O+ (acid-catalyzed)

NaOH/H2O (base-catalyzed)

enol → ketone via enol favored (keto form)

base deprotonates → reprotonates → enolate → tautomer

NaBH4, Ch3OH

or

(1) LiAlH4, (2) H2O

or

H2, Pd-C

aldehydes/ketones → 1°/2° Alcohol

NaBH4, Ch3OH

H2, Pd-C (1 equiv)

H2, Pd-C (excess)

reduction of C=O to OH

reduction of C=C only

reduction of both pi bonds

(1) (S or R) CBS reagent, (2) H2O

S → R 2° Alcohol

R → S 2° Alcohol

(1) LiAlH4, (2) H2O

or

(1) LiAlH[OC(Ch3)3]3, (2) H2O

acid chloride → 1° Alcohol

acid chloride → aldehyde

(1) LiAlH4, (2) H2O

(1) DIBAL-H, (2) H2O

ester → 1° Alcohol

ester → aldehyde

(1) LiAlH4, (2) H2O

carboxylic acid → 1° Alcohol

amide → amine

CrO3, Na2Cr2O7, K2Cr2O7, KMnO4

or

Ag2O, NH4OH

aldehyde → carboxylic acid

preparing organolithium reagents

R-X + 2 LI → R-Li + LiX

preparing grignard reagents

R-X + Mg → R-Mg-X

preparing organocuprate reagents

2 R-Li + CuI → R2Cu- Li+ + LiI

Na+ -NH2

R-Li

acetylene → sodium acetylide

acetylene → lithium acetylide

organometallics as bases

R-M + H-O-R → R-H + M(+) + (-)O-R

(1) R'MgX or R'Li, (2) H2O

aldehyde/ketone → 1, 2, 3° Alcohol

(1) R"Li or R"MgX (2 equiv), (2) H2O

esters → 3° Alcohol

(1) R"Li or R"MgX (2 equiv), (2) H2O

(1) R'2CuLi, (2) H2O

acid chloride → 3° Alcohol

acid chloride → ketone

(1) CO2, (2) H3O+

R-MgX → carboxylic acid

(1) RLi, RMgX, or R2CuLi, (2) H2O

epoxide → alcohol

(1) R'Li or R'MgX, (2) H2O

or

(1) R'2CuLi, (2) H2O

a,B-unsaturated aldehyde/ketone → allylic alcohol (1,2)

a,B-unsaturated aldehyde/ketone → ketone (1,4)

alcohol (ROH) + TBS

TBS ether (R-O-TBS)

Bu4N+ F-

R-O-TBS → ROH + F-TBS