Petersen olefination

Silyloxide eliminations (Petersen olefination) also proceed readily and regiospecifically to give olefins. When base is used to produce die oxyanion, the elimination occurs widi syn stereochemistry. If an acid is used to promote the elimination, it occurs in an anti fashion, leading to die opposite olefin stereochemistry. This is a very useful way to generate either a Z or E olefin from die same starting material. 

J. Huang, E. D. Stevens, S. P. Nolan, and J. L. Petersen, Olefin Metathesis-Active Ruthenium Complexes Bearing a Nucleophilic Carbene Ligand, J. Am. Chem. Soc. 121, 2674-2678 (1999). 

These furfliryl alcohols can be produced in either enantiomeric form via asymmetric catalysis. Our preferred method for the asymmetric synthesis of these fiiran alcohols 4.2 is by the highly enantioselective Noyori reduction of achiral acylfurans 4.1 (Scheme 4). Alternatively fiirfurly alcohols like 4.4 can be prepared by the Sharpless asymmetric dihydroxylation of vinylfuran 4.3. Key to this later approach was the recognition that vinylfuran 4.3 could be made by a Petersen olefination reaction. 

Focusing on completion of the synthesis, we examined one-carbon chain lengthening strategies based on masked acyl cyanides and on modified Petersen olefinations. Preliminary experiments were not promising, and we considered the modification of our scheme in order to bypass the need for homologation. 

Minnie, O. R., Petersen, F. W., and Samadi, F. R. 2003. Effect of 1-hexene extraction on the COD process conversion of olefins to distillate. Paper presented at the South African Chemical Engineering Congress, Sun City, P083. 

Thus, the alkoxides generated from silyl derivatives (150) undergo the Petersen reaction yielding olefins (Scheme 56) " ... 

Olefin binding and counteranion binding are competitive. This supposition is supported by experimental work from the Jordan lab. As shown in Figure 9 Wu. Jordan, and Petersen" find the olefin binding affinities of coordinated vinyl alkoxides to be strongly dependent upon the length of the alkyl chain (n). For... 

Huang, J., Stevens, E.D., Nolan, S.R and Petersen, J.L. (1999) Olefin metathesis-active ruthenium complexes bearing a nucleophUic carbene ligand. J. Am. Chem. Soc., 121, 2674-8. 

Huang J, Stevens ED, Nolan SP, Petersen JL. Olefin metathesis-active ruthenium complexes beating a nucleophUic carbene ligand. J Am Chem Soc. 1999 121(12) 2674-2678. 

Faulkner, D. J. Petersen, M. R. Application of the Claisen Rearrangement to the Synthesis of Trans Trisubstituted Olefinic Bonds. Synthesis of Squalene and Insect Juvenile Hormone J. Am. Chem. Soc. 1973, 95, 553. 

Johnson WS, Werthemann L, Bartlett WR, Brocksom TJ, Li T-T, Faulkner DJ, Petersen MR. Simple stereoselective version of the Claisen rearrangement leading to trans-tri-suhstituted olefinic bonds. Synthesis of squalene. J. Am. Chem. Soc. 1970 92(3) 741-743. 

This stereoselective version of the Claisen rearrangement leading to tro/is-trisubstituted olefinic bonds has been developed by W. S. Johnson, L. Werthmann, W. R. Bartlett, T. j. Brocksom, T.-t. Li, D. j. Faulkner and M. R. Petersen, J. Amer. Chem. Soc., 92, 741 (1970). The reaction evidently involves formation of a mixed orthoester (i), and loss of ethanol to form the ketene acetal (ii) which rearranges to the olefinic ester (iii). 

Delp SA, Munro-Leighton C, Goj LA, Ramirez MA, Gunnoe TB, Petersen JL, Boyle PD (2007) Addition of S-H bonds across electron-deficient olefins catalyzed by well-defined copper(I) thiolate complexes. Inorg Chem 46 2365-2367... 

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