Asymmetric Alkylation of Enolates

Last updated
Save as PDF

Page ID: 13732

\( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \) \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)\(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\) \(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\)\(\newcommand{\AA}{\unicode[.8,0]{x212B}}\)

Meyers, A. I.; Knaus, G.; Kamata, K.; Ford, M. E. J. Am. Chem. Soc. 1976, 98, 567-576.

Evans, D. A.; Takacs, J. M.; Tetrahedron Lett. 1980, 21, 4233.

Sonnet, P.; Heath, R. R. J. Org. Chem. 1980, 45, 3137.

Evans, D. A.; Dow, R. L.; Shih, T. L.; Takacs, J. M.; Zahler, R. J. Am. Chem. Soc. 1990, 112, 5290-5313.

Evans, D. A.; Ennis, M. D.; Mathre, D. J. J. Am Chem. Soc. 1982, 104, 1737-1739.

Evans, D. A.; Bartroli, J.: Shih, T. L. J. Am. Chem. Soc. 1981, 103, 2127-2129.

Evans, D. A.; Ennis, M. D.; Mathre, D. J. . J. Am. Chem. Soc. 1982, 104, 1737-1739.

Evans, D. A.; Ennis, M. D.; Mathre, D. J. . J. Am. Chem. Soc. 1982, 104, 1737-1739.

Decicco, C. P.; Grover, P. J. Am. Chem. Soc. 1996, 61, 3534-3541.

see also: Williams, D. R.; McGill, J. M. J. Org. Chem. 1990, 55, 3447-3459.

Evans, D. A.; Urpi, F.; Somers, T. C.; Clark, J. S.; Bilodeau, M. T. J. Am. Chem. Soc. 1990, 112, 8215-8216.

Evans, D. A.; Ennis, M. D.; Mathre, D. J. J. Am. Chem. Soc. 1982, 104, 1737-1739.

Evans, D. A.; Morissey, M. M.; Dorow, R. L. J. Am. Chem. Soc. 1985, 107, 4346-4348.

Evans, D. A.; Britton, T. C.; Ellman, J. A.; Dorow, R. L. J. Am. Chem. Soc. 1990, 112,

Morales, M.R.; Mellem, K.T.; Myers, A.G. Angew. Chem. Int. Ed., 2012, 51, 4568–4571.

Preparation of Pseudoephedrine and Pseudoephenamine Amides

Myers, A. G.; Yang, B. H.; Chen, H.; McKinstry, L.: Kopecky, D. J.; Gleason, J. L. J. Am. Chem. Soc. 1997, 119, 6496-6511.

Morales, M.R.; Mellem, K.T.; Myers, A.G. Angew. Chem. Int. Ed., 2012, 51, 4568–4571.

Alkylation of Pseudoephenamine and Pseudoephedrine Amides

Myers, A. G.; McKinstry, L. J. Org. Chem. 1996, 61, 2428.

Askin, D.; Volante, R. P.; Ryan, K. M.; Reamer, R. A.; Shinkai, I. Tetrahedron Lett. 1988, 29, 4245.

Diastereoselective Alkylation Reactions

Hydrolysis of Alkylation Products

Morales, M.R.; Mellem, K.T.; Myers, A.G. Angew. Chem. Int. Ed., 2012, 51, 4568–4571.

Myers, A. G.; Yang, B. H.; Chen, H.; McKinstry, L.; Kopecky, D. J.; Gleason, J. L. J. Am. Chem. Soc. 1997, 119, 6496-6511.

Reduction of Alkylation Products

Myers, A. G.; Yang, B. H.; Kopecky, D. J. Tetrahedron Lett. 1996, 37, 3623.Myers, A. G.; Yang, B. H.; Chen, H.; Kopecky, D. J. Synlett 1997, 5, 457.

Myers, A. G.; Yang, B. H.; Chen, H.; McKinstry, L.; Kopecky, D. J.; Gleason, J. L. J. Am. Chem. Soc. 1997, 119, 6496-6511.

Brown, H. C.; Tsukamoto, A. J. Am. Chem. Soc. 1964, 86, 1089.Addition of Alkyllithium Reagents to form Ketones
Myers, A. G.; Yang, B. H.; Chen, H.; Kopecky, D. J. Synlett 1997, 5, 457-459.

Construction of Quaternary Centers

Enolization–Alkylation

Kummer, D. A.; Chain, W. J.; Morales, M. R.; Quiroga, O.; Myers, A. G. J. Am. Chem. Soc. 2008, 130, 13231–13233.

Conjugate Addition-Aklyation

Morales, M. R.; Mellem, K. T.; Myers, A. G. Angew. Chem. Int. Ed., 2012, 51, 4568–4571.

E. Reyes, J. L. Vicario, L. Carrillo, D. Badia, A. Iza, U. Uria, Org. Lett. 2006, 8, 2535–2538.

Transformations of \(\alpha\)-quaternary pseudoephenamine and pseudoephedrine amides

Hydrolysis of \(\alpha\)-quaternary alkylation products

Kummer, D. A.; Chain, W. J.; Morales, M. R.; Quiroga, O.; Myers, A. G. J. Am. Chem. Soc. 2008, 130, 13231–13233.

Addition of alkyllithium reagents to form ketones

Reduction to form Aldehydes

LAB reduction to form primary alcohols

Helmchen camphor-derived auxiliaries

Schmierier, R.; Grotemeier, G.; Helmchen, G.; Selim, A. Angew. Chem., Int. Ed. Engl. 1981, 20, 207-208.

Oppolzer camphorsultam auxiliaries in asymmetric alkylation:

Oppolzer, W.; Moretti, R.; Thomi, S. Tetrahedron Lett. 1989, 30, 5603-5606.
Enders, D. In Asymmetric Synthesis; Morrison, J. D.; Academic Press: New York, 1984; Vol. 3, Chapter 4.

Enders, D.; Hundertmark, T.; Lazny, R. Syn. Comm. 1999, 29, 27-33.

Lim, D.; Coltart, D. M. Angew. Chem., Int. Ed. Engl. 2008, 47, 5207–5210.• An early, remarkable result from the Merck Process group:

Dolling, U.; David, P.; Grabowski, E. J. J. J. Am. Chem. Soc. 1984, 106, 446-447.

O' Donnell, M. J.; Bennett, W. D.; Wu, S. J. Am. Chem. Soc. 1989, 111, 2353-2355.Cl

Corey, E. J.; Xu, F.; Noe, M. C. J. Am. Chem. Soc. 1997, 119, 12414-12415.

Imai, M.; Hagihara, A.; Kawasaki, H.; Manabe, K.; Koga, K. J. Am. Chem. Soc. 1994, 116, 8829-8830.Myers Catalytic Methods for Asymmetric Alkylation Chem 115