476 CHAPTER 12 Reactions of Alcohols, Ethers, Epoxides, and Sulfur-Containing Compounds- Reaction of an aryl,benzyl, or vinyl halideor triflatewith a stannane: the Stille reaction (Section 12.12).
- Reaction of an aryl,benzyl, or vinyl halidewith an organoborane: the Suzuki reaction (Section 12.12).
NaOHBr R
+ RBOONaOHBr CH CHR
+ RCH CH BOOPd(PPh 3 ) 4Pd(PPh 3 ) 4THFR
SnR 4OTf
+THFPd(PPh 3 ) 4Pd(PPh 3 ) 4CH CH 2
CH 2 CHSnR 3Br
+Key Terms
alcohol (p. 437)
alkyl tosylate (p. 444)
alkyl triflate (p. 444)
arene oxide (p. 457)
coupling reaction (p. 470)
crown ether (p. 462)
dehydration (p. 445)
epoxide (p. 454)
ether (p. 451)
Gilman reagent (p. 470)Grignard reagent (p. 467)
Heck reaction (p. 472)
inclusion compound (p. 462)
molecular recognition (p. 463)
organocuprate (p. 470)
organolithium compound (p. 467)
organomagnesium compound (p. 467)
organometallic compound (p. 466)
oxirane (p. 454)
phase-transfer catalyst (p. 463)ring-expansion rearrangement (p. 447)
Stille reaction (p. 472)
sulfide (p. 464)
sulfonate ester (p. 443)
sulfonium salt (p. 464)
Suzuki reaction (p. 472)
thioether (p. 464)
thiol (p. 464)
transmetallation (p. 470)Problems
- Give the product of each of the following reactions:
a. f.b. g.c. h.d. i.e. j. Sn(CH 2 CH 2 CH 3 ) (^4) THF
Br
- Pd(PPh 3 ) 4
Et 3 N
CH 2 CH 2
I
Pd(PPh 3 ) 4
- H+, H 2 O
- ethylene oxide
CH 3 CH 2 CH C + CH 3 OH CH 2 MgBr
H+OCH 3CH 3CH 3 CHCH 2 CH 2 OHCH 3pyridineSOCl 2
CH 3 CHCH 2 CH 2 OH2.- p-toluenesulfonyl chloride
CH 3 O−CH 3 CH 2 CH 2 CH 2 OH ∆H 2 SO 4
pyridineCH 3 CH 2 CH 2 CH 2 OH + PBr 3CH 3 CH 2 CH C
OCH 3CH 3+ CH 3 OHCH 3 O−
CH 3 CH 2 CH 2 OH O- CH 3 CO−
- methanesulfonyl chloride
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