Page 1104 - Advanced Organic Chemistry Part B - Reactions & Synthesis

1080 Scheme 12.7. Enantioselective Osmium-Catalyzed Dihydroxylation of Alkenes

CHAPTER 12 1 a K 2 OsO (OH) , OH
2
2
Oxidations (DHQD) -PHAL PhO
2
PhOCH CH CH2 CH 2 OH
2
6
K 3 Fe(CN) , K CO 3
2
88% e.e.
OH
2 b HO
2
1 mol % K 2 OsO (OH) 2 CH OH
HO CH CH2 2
(DHQD) -DPPYR
2
Fe(CN) , K CO
K 3 6 2 3 88% yield,
90% e.e.
3 c K OsO (OH) , OH
2
2
2
DHQ-PHAL
E-C H O CCH CH CH CH(CH ) CH 3 O O
2
2
2
2 11
2 5
K Fe(CN) , K CO , (CH ) CH 3
2 11
3
2
6
3
CH SO NH 2
2
3
82% yield,
4 d 95% e.e.
OsO (OH) , HO
0.2 mol % K 2 2 4
0.25 mol % (DHQD) -PHAL
2
N-methylmorpholine-N-oxide
OH 76% yield,
99% e.e.
5 e OH
2
0.01 mol % K 2 OsO ,
O CCH 3 1 mol % (DHQ) -PYDZ OH O CCH 3
2
2
2
K Fe(CN) 6 , K 2 CO 3
3
76% yield,
>95% e.e.
6 f CH 3 K OsO (OH) , 1 mol % OH CH 3
4
2
2
(DHQD) -PHAL
NCH Ph 2 NCH 2 Ph
2
Ph Ph
2
2
CH 3 SO NH , 97% yield,
O K Fe(CN) OH O
7 g 3 6 98% e.e.
1 mol % K OsO (OH) , CH 3
2
2
CH 3 (DHQ)2-PHAL 4 (CH ) CHCH OH
(CH ) CHCH 2 C CH 2 K 3 Fe(CN) 6 3 2 2 CH OH
3 2
2
99%
8 h 1 mol % K 2 OsO 2 (OH) 4 , HO
E-CH CH CHCH 2 CO CH 3 (DHQ)2-PHAL O
3
2
K Fe(CN) 6 CH 3 O
3
48% yield,
80% e.e.
9 i OH
1 mol % K 2 OsO 2 (OH) 4
(DHQ) -PHAL
2
C H O CO CH 3 C H O CO CH 3
2 5
2
2 5
2
K 3 Fe(CN) 6 OH
93% yield,
97.5% e.e.
a. Z.-M. Wang, X.-L. Zhang, and K. B. Sharpless, Tetrahedron Lett., 34, 2267 (1993).
b. Z.-M. Wang and K. B. Sharpless, Tetrahedron Lett., 34, 8225 (1993).
c. Z.-M. Wang, X.-L. Zhang, K. B. Sharpless, S. C. Sinha, A. Sinha-Bagchi, and E. Keinan, Tetrahedron Lett., 33,
6407 (1992).
d. H. T. Chang and K. B. Sharpless, J. Org. Chem., 61, 6456 (1996).
e. E. J. Corey, M. C. Noe, and W.-C. Shieh, Tetrahedron Lett., 34, 5995 (1993).
f. Y. L. Bennani and K. B. Sharpless, Tetrahedron Lett., 34, 2079 (1993).
g. H. Ishibashi, M. Maeki, J. Yagi, M. Ohba, and T. Kanai, Tetrahedron, 55, 6075 (1999).
h. T. Berkenbusch and R. Bruckner, Tetrahedron, 54, 11461 (1998).
i. T. Taniguchi, M. Takeuchi, and K. Ogasawara, Tetrahedron: Asymmetry, 9, 1451 (1998).