Organic Chemistry

Summary of Reactions 475

6. Ring-opening reactions of epoxides(Section 12.7)


7. Reactions of arene oxides: ring opening and rearrangement (Section 12.8).


8. Reactions of thiols, sulfides, and sulfonium salts (Section 12.10).


9. Reaction of a Grignard reagentwith an epoxide(Section 12.11).


10. Reaction of a Gilman reagentwith an alkyl halide(Section 12.12).


11. Reaction of an aryl,benzyl, or vinyl halideor triflatewith an alkene: the Heck reaction (Section 12.12).

+

OTf

+ CH 2 CH 2

CH CH 2

(CH 3 CH 2 ) 3 N

Pd(PPh 3 ) 4

(CH 3 CH 2 ) 3 N

Pd(PPh 3 ) 4

Br

THF

RLi + CuI R 2 CuLi

THF

CH 3 CH 2 CH 2 X ++

X = Cl, Br, or I

R 2 CuLi CH 3 CH 2 CH 2 R RCu + LiX

2 + LiI

Gilman reagent

diethyl ether

a Grignard reagent

product alcohol contains two more carbons than the Grignard reagent

Mg

H+

RMgBr + H 2 C

RBr RMgBr

O

CH 2 RCH 2 CH 2 O− RCH 2 CH 2 OH

2 RSH + Hg^2 + RS Hg SR + 2 H+

RS− RSR′

RSR R′IIRSR −

R′

Br

+

+ + Br−

+

RSR Y− RY RSR

R

+ +

R′

+

++Y−

OH

Y OH

O

H+

CH 3 OH

under acidic conditions, the nucleophile

C attacks the more substituted ring-carbon

H 3 C

H 3 C

H 3 C CH 3

CH 3 CCH 2 OH

O OCH 3

CH 2

C

H 3 C

O

CH 2

CH 3 O−

CH 3 OH

under basic conditions, the nucleophile

attacks the less sterically hindered ring-carbon

CH 3

CH 3 CCH 2 OCH 3

OH

BRUI12-437_480r3 27-03-2003 11:51 AM Page 475