Chelation-controlled additions to α-silyloxy aldehydes: an autocatalytic approach.

The Felkin-Anh model has been widely accepted to describe stereochemical outcomes in nucleophilic additions to α-silyloxy carbonyl compounds. Herein, it is demonstrated that chelation-controlled additions can be performed using dialkylzinc reagents in the presence of chlorotrimethylsilane with good to excellent diastereoselectivities. Ethyl zinc chloride, the Lewis acid responsible for promoting chelation, is generated in situ in an autocatalytic fashion. This approach circumvents its use in stoichiometric amounts.

[1]  S. P. Fletcher,et al.  Mechanisms of autocatalysis. , 2013, Angewandte Chemie.

[2]  P. Carroll,et al.  Synthesis of Chiral N‐Sulfonyl and N‐Phosphinoyl α‐Halo Aldimine Precursors , 2013 .

[3]  P. Carroll,et al.  Chelation-controlled addition of organozincs to α-chloro aldimines. , 2012, Journal of the American Chemical Society.

[4]  D. Blackmond,et al.  Observation of a transient intermediate in Soai's asymmetric autocatalysis: insights from 1H NMR turnover in real time. , 2012, Angewandte Chemie.

[5]  P. Walsh,et al.  Diastereoselective chelation-controlled additions to β-silyloxy aldehydes. , 2012, Organic letters.

[6]  P. Walsh,et al.  Efficient approaches to the stereoselective synthesis of cyclopropyl alcohols. , 2012, Accounts of chemical research.

[7]  P. Walsh,et al.  Highly diastereoselective chelation-controlled additions to α-silyloxy ketones. , 2011, Journal of the American Chemical Society.

[8]  C. Lorenz,et al.  Elucidating the origin of diastereoselectivity in a self-replicating system: selfishness versus altruism. , 2011, Chemistry.

[9]  Barbara Odell,et al.  Unusual inverse temperature dependence on reaction rate in the asymmetric autocatalytic alkylation of pyrimidyl aldehydes. , 2010, Journal of the American Chemical Society.

[10]  P. Walsh,et al.  Overriding Felkin control: a general method for highly diastereoselective chelation-controlled additions to alpha-silyloxy aldehydes. , 2010, Journal of the American Chemical Society.

[11]  P. Carroll,et al.  One-pot catalytic enantio- and diastereoselective syntheses of anti-, syn-cis-disubstituted, and syn-vinyl cyclopropyl alcohols. , 2010, Journal of the American Chemical Society.

[12]  D. Philp,et al.  A simple synthetic replicator amplifies itself from a dynamic reagent pool. , 2008, Angewandte Chemie.

[13]  M. Mauksch,et al.  Evidence of asymmetric autocatalysis in organocatalytic reactions. , 2007, Angewandte Chemie.

[14]  Douglas Philp,et al.  Reciprocal template effects in a simple synthetic system. , 2006, Chemical communications.

[15]  Douglas Philp,et al.  Design and implementation of a highly selective minimal self-replicating system. , 2006, Angewandte Chemie.

[16]  Toshio Suzuki,et al.  Total synthesis of valeriananoids A, B, and C via autocatalytic diastereoselective domino Michael reaction , 2006 .

[17]  Hiroshi Iwamura,et al.  Thermodynamic control of asymmetric amplification in amino acid catalysis , 2006, Nature.

[18]  A. Haudrechy,et al.  Alkynylation of chiral aldehydes: alkoxy-, amino-, and thio-substituted aldehydes. , 2006, Chemical reviews.

[19]  M. Bochmann,et al.  Synthesis and Crystal Structure of Ethyl Zinc Chloride , 2006 .

[20]  D. Philp,et al.  Specific autocatalysis in diastereoisomeric replicators. , 2005, Organic letters.

[21]  Hiroshi Iwamura,et al.  Amplification of enantiomeric excess in a proline-mediated reaction. , 2004, Angewandte Chemie.

[22]  Toshio Suzuki,et al.  Autocatalytic domino Michael reaction leading to bicyclo[2.2.2]octane-2,5-dione derivatives. , 2004, Organic letters.

[23]  Kenso Soai,et al.  Amplification of chirality from extremely low to greater than 99.5 % ee by asymmetric autocatalysis. , 2003, Angewandte Chemie.

[24]  Kenso Soai,et al.  Asymmetric synthesis of pyrimidyl alkanol without adding chiral substances by the addition of diisopropylzinc to pyrimidine-5-carbaldehyde in conjunction with asymmetric autocatalysis , 2003 .

[25]  D. Blackmond,et al.  Origins of asymmetric amplification in autocatalytic alkylzinc additions. , 2001, Journal of the American Chemical Society.

[26]  D. Philp,et al.  Transfer of stereochemical information in a minimal self-replicating system. , 2001, Organic letters.

[27]  O. Reiser,et al.  Around and beyond Cram's Rule. , 1999, Chemical reviews.

[28]  Kenso Soai,et al.  Practically Perfect Asymmetric Autocatalysis with (2-Alkynyl-5-pyrimidyl)alkanols. , 1999, Angewandte Chemie.

[29]  K. Soai,et al.  One-pot asymmetric autocatalytic reaction with remarkable amplification of enantiomeric excess , 1997 .

[30]  H. Morioka,et al.  Enantioselective synthesis of chiral 5-carbamoyl-3-pyridyl alcohols by asymmetric autocatalytic reaction , 1996 .

[31]  Kenso Soai,et al.  Highly Enantioselective Catalytic Asymmetric Automultiplication of Chiral Pyrimidyl Alcohol , 1996 .

[32]  Kenso Soai,et al.  Asymmetric autocatalysis and amplification of enantiomeric excess of a chiral molecule , 1995, Nature.

[33]  E. Wintner,et al.  Self-Replicating Molecules: A Second Generation , 1994 .

[34]  S. Frye,et al.  Chelates as intermediates in nucleophilic additions to alkoxy ketones according to Cram's rule (cyclic model) , 1992 .

[35]  S. Frye,et al.  Rapid-injection nuclear magnetic resonance investigation of the reactivity of .alpha.- and .beta.-alkoxy ketones with dimethylmagnesium: kinetic evidence for chelation , 1987 .

[36]  N. Anh.  Regio- and stereo-selectivities in some nucleophilic reactions , 1980 .

[37]  O. Eisenstein,et al.  Orbital factors and asymmetric induction , 1973 .

[38]  D. Cram,et al.  Studies in Stereochemistry. XXX. Models for Steric Control of Asymmetric Induction1 , 1959 .

[39]  D. Cram,et al.  Studies in Stereochemistry. X. The Rule of “Steric Control of Asymmetric Induction” in the Syntheses of Acyclic Systems , 1952 .

[40]  H. Morioka,et al.  Highly enantioselective synthesis of a chiral 3-quinolylalkanol by an asymmetric autocatalytic reaction , 1996 .

[41]  Julius Rebek,et al.  Self-replicating system , 1990 .

[42]  H. Hori,et al.  Asymmetric self-catalytic reaction. Self-production of chiral 1-(3-pyridyl)alkanols as chiral self-catalysts in the enantioselective addition of dialkylzinc reagents to pyridine-3-carbaldehyde , 1990 .

[43]  G. Bazsa,et al.  Dependence of the inflection time on the initial concentrations in autocatalytic reactions. Maxima, minima and ‘anomalous changes’ , 1988 .

[44]  Nguyên Trong Anh,et al.  Induction asymetrique 1–2: comparaison ab initio des modeles de cram, de cornforth, de karabatsos et de felkin. , 1976 .

[45]  M. Chérest,et al.  Torsional strain involving partial bonds. The stereochemistry of the lithium aluminium hydride reduction of some simple open-chain ketones , 1968 .

[46]  F. Frank,et al.  On spontaneous asymmetric synthesis. , 1953, Biochimica et biophysica acta.