Page 386 - Advanced Organic Chemistry Part B - Reactions & Synthesis

358 General References

CHAPTER 4
nd
P. B. de la Mare and R. Bolton, Electrophilic Additions to Unsaturated Systems,2 ed., Elsevier, New York,
Electrophilic Additions
to Carbon-Carbon 1982.
Multiple Bonds N. Krause and A. S. K. Hashmi, eds., Modern Allene Chemistry, Wiley-VCH, Weinheim, 2004.
C. Paulmier, Selenium Reagents and Intermediates in Organic Synthesis, Pergamon, Oxford, 1986.
S. Patai, ed., The Chemistry of Double-Bonded Functional Groups, Supplement A, Vol 2, John Wiley & Sons,
New York, 1988.
S. Patai, ed., The Chemistry of Sulphenic Acids and Their Derivatives, Wiley, Chichester, 1990.
S. Patai, editors, The Chemistry of Trible-Bonded Functional Groups, Supplement C2, John Wiley & Sons,
New York, 1994.
S. Patai, and Z. Rappoport, eds., The Chemistry of Organic Selenium and Tellurium Compounds, John
Wiley & Sons, New York, 1986.
A. Pelter, A. Smith, and H. C. Brown, Borane Reagents, Academic Press, 1988.
P. V. Ramachandran and H. C. Brown, Organoboranes for Synthesis, American Chemical Society,
Washington, 2001.
H. F. Schuster and G. M. Coppola, Allenes in Organic Synthesis, Wiley, New York, 1984.
P. J. Stang and F. Diederich, eds., Modern Acetylene Chemistry, VCH Publishers, Weinheim, 1995.

Problems

(References for these problems will be found on page 1277.)

4.1. Predict the products, including regio- and stereochemistry, for the following
reactions:

(a) (b) HOBr
CH 3 CH CH 2 +O 2 N SCl CH 2
NO 2
(c) 1) disiamylborane (d) IN 3
(CH 3 ) 2 C CHCH 3 CH 3 CH 2 CH 2 CH 2 CH CH 2
–
2) H 2 O 2 , HO
(e) IN 3 (f) IN 3
(CH 3 ) 3 CCH CHCH 3 C 6 H 5 CH CHCH(OCH 3 ) 2
(g) PhSeBr NaHCO 3 (h) Hg(OAc) 2 H 2 O, NaHCO 3
HC CCH 2 CH 2 CO 2 H
OSi(CH 3 ) 3
ether, –78°C H 2 O CH 2 Cl 2 10 min
(i) 1) Hg(OAc) 2 (j) I 2 , NaN 3
H 2 C CHCH 2 CH 2 CH 2 CH 2 OH
CHCl 3 ,
2) NaBH 4
crown ether
(k) NOCl (l) PhSCl, Hg(OAc) 2
C 14 H 19 NOS
LiClO 4 , CH 3 CN
(m) I 2
PhCHCH 2 CO 2 H
CH 3 CN
CH CH 2

4.2. Bromination of 4-t-butylcyclohexene in methanol gives a 45:55 mixture of
two compounds, each of composition C H BrO. Predict the structure and
11
21
stereochemistry of these two products. How would you confirm your prediction?