Total Synthesis of Prelaureatin

Abstract

Total synthesis of prelaureatin, which is an 8-membered cyclic ether isolated from red alga Laurencia nipponica, has been achieved through a process including stereoselective introduction of two allyl groups starting from galactose pentaacetate, cleavage of the hexose ring, and transformation of an acyclic triene into an oxocene by selective ring-closing metathesis.

Key words

total synthesis - stereoselective synthesis - natural products - ethers - metathesis

References

• 1 Fukuzawa A. Takasugi Y. Murai A. Tetrahedron Lett.  1991,  32:  5597 
• 2 Irie T. Izawa M. Kurosawa E. Tetrahedron  1970,  26:  851 
• 3 Fukuzawa A. Kurosawa E. Tetrahedron Lett.  1979,  32:  2797 
• 4 Watanabe K. Umeda K. Miyakado M. Agric. Biol. Chem.  1989,  53:  2513 
• 5 Kulkarni SK. Kurosawa E. Indian. J. Exp. Biol.  1981,  19:  101 
• 6a Fukuzawa A. Aye M. Takasugi Y. Nakamura M. Tamura M. Murai A. Chem. Lett.  1994,  2307 
• 6b Ishihara J. Shimada Y. Kanoh N. Takasugi Y. Fukuzawa A. Murai A. Tetrahedron  1997,  53:  8371 
• 7 For the first total syntheses of 1 and 4, see: Crimmins MT. Tabet EA. J. Am. Chem. Soc.  2000,  122:  5473 
• For recent reviews on olefin metathesis, see:
• 8a Grubbs RH. Miller SJ. Fu GC. Acc. Chem. Res.  1995,  28:  446 
• 8b Schuster M. Blechert S. Angew. Chem., Int. Ed. Engl.  1997,  36:  2067 ; Angew. Chem. 1997, 109, 2124
• 8c Grubbs RH. Chang S. Tetrahedron  1998,  54:  4413 
• 8d Armstrong SK. J. Chem. Soc., Perkin Trans. 1  1998,  371 
• 8e Blechert S. Pure Appl. Chem.  1999,  71:  1393 
• 8f Fürstner A. Angew. Chem. Int. Ed.  2000,  39:  3013 
• 9 For a recent review on cyclic ethers, see: Elliot MC. J. Chem. Soc., Perkin Trans. 1  1998,  4175 
• 10a Uenishi J. Kawahama R. Yonemitsu O. Tsuji J. J. Org. Chem.  1996,  61:  5716 
• 10b Uenishi J. Kawahama R. Yonemitsu O. Tsuji J. J. Org. Chem.  1998,  63:  8965 
• 10c See, also: Fujiwara K. Awakura D. Tsunashima M. Nakamura A. Honma T. Murai A. J. Org. Chem.  1999,  64:  2616 
• 11 Another approach to cyclize a triene precursor into a medium-sized cyclic ether by RCM has been reported, where the modest selectivity has been observed: Crimmins MT. Emmitte KA. Choy AL. Tetrahedron  2002,  58:  1817 
• 12 Giannis A. Sandhoff K. Tetrahedron Lett.  1985,  26:  1479 
• 13a Omura K. Swern D. Tetrahedron  1978,  34:  1651 
• 13b Mancuso AJ. Huang S.-L. Swern D. J. Org. Chem.  1978,  43:  2480 
• 13c Mancuso AJ. Swern D. Synthesis  1981,  165 
• 14 Henry KJ. Grieco PA. Jagoe CTJ. Tetrahedron Lett.  1992,  33:  1817 
• 15a Shimizu T. Hiranuma S. Nakata T. Tetrahedron Lett.  1996,  37:  6145 
• 15b Shimizu T. Ohzeki T. Hiramoto K. Hori N. Nakata T. Synthesis  1999,  1373 
• 16a Hooz J. Gilani SSH. Can. J. Chem.  1968,  46:  86 
• 16b Murai A. Murase H. Matsue H. Masamune T. Tetrahedron Lett.  1977,  2507 
• 16c Tsushima K. Murai A. Tetrahedron Lett.  1992,  33:  4345 
• 17a Schmidt SP. Brooks DW. Tetrahedron Lett.  1987,  28:  767 
• 17b Brats M. Bullock WH. Overman LE. Takemoto T. J. Am. Chem. Soc.  1995,  117:  5958 
• 17c See, also: Fujiwara K. Kobayashi M. Awakura D. Murai A. Synlett  2000,  1187 
• 18 Scholl M. Ding S. Lee CW. Grubbs RH. Org. Lett.  1999,  1:  953 
• 19 Fu GC. Nguyen ST. Grubbs RH. J. Am. Chem. Soc.  1993,  115:  9856 
• 20 Sonogashira K. Tohda Y. Hagihara N. Tetrahedron Lett.  1975,  4467