Enantioselective Synthesis of (R)-Propylene Carbonate from Ethyl (S)-Lactate

Abstract

We report a three-step synthesis of (R)-propylene carbonate from inexpensive, chiral ethyl (S)-lactate. The synthesis involves a borohydride ester reduction and an unusual intramolecular displacement reaction by a carbonate anion. The procedure is simple and reliable, resulting in (R)-propylene carbonate in approximately 60% overall yield with ≥98% ee.

Key words

propylene carbonate - cyclic carbonate formation - borohydride reductions - nucleophilic addition - chiral pool

References

• 1a Schultze LM. Chapman HH. Dubree NJP. Jones RJ. Kent KM. Lee TT. Louie MS. Postich MJ. Prisbe EJ. Rohloff JC. Yu RH. Tetrahedron Lett.  1998,  39:  1853 
• 1b Munger JD, Rohloff JC, and Schultze LM. inventors; WO  9905150. 
• 1c Barral K. Priet S. Sire J. Neyts J. Balzarini J. Canard B. Alvarez K. J. Med. Chem.  2006,  49:  7799 
• 2a Basel Y. Hassner A. J. Org. Chem.  2000,  65:  6368 
• 2b Rannard SP. Davis NJ. Org. Lett.  1999,  1:  933 
• From optically active propylene oxide:
• 3a 73-98% ee: Kisch H. Millini R. Wang I.-J. Chem. Ber.  1986,  119:  1090 
• From racemic propylene oxide:
• 3b 27-85% ee: Chen S.-W. Kawthekar RB. Kim G.-J. Tetrahedron Lett.  2007,  48:  297 
• 3c 14-83% ee: Berkessel A. Brandenburg M. Org. Lett.  2006,  8:  4401 
• 3d 3-70% ee: Lu X.-B. Liang B. Zhang Y.-J. Tian Y.-Z. Wang M.-Y. Bai C.-X. Wang H. Zhang R. J. Am. Chem. Soc.  2004,  126:  3732 
• 4 Hillis LR. Ronald RC. J. Org. Chem.  1981,  46:  3348 
• 5 Burkard U. Effenberger F. Chem. Ber.  1986,  119:  1594 
• 6a Kaupp G. Matthies D. De Vrese C. Chem.-Ztg.  1989,  113:  219 
• 6b Kurov VI. Trudy Leningrad. Tekstil. Inst.  1955,  6:  99 ; Chem. Abstr. 1959, 53, 6424
• 7a Cella JA. Bacon SW. J. Org. Chem.  1984,  49:  1122 
• 7b Lissel M. Dehmlow EV. Chem. Ber.  1981,  114:  3348 
• 8 Johnston BD. Slessor KN. Can. J. Chem.  1979,  57:  233 
• 9 The Chemist’s Companion   Gordon G. Ford R. J. Wiley; New York: 1972.  p.61 
• 10a Mori K. Senda S. Tetrahedron  1985,  41:  541 
• 10b Seebach D. Seuring B. Helv. Chim. Acta  1977,  60:  1175