Mixed Aggregates of 1-Methoxyallenyllithium with Lithium Chloride

Pratt, Lawrence M.; Dixon, Darryl D.; Tius, Marcus A.

doi:10.1002/open.201402025

Mixed Aggregates of 1-Methoxyallenyllithium with Lithium Chloride

Journal Article · Tue Nov 18 23:00:00 EST 2014 · ChemistryOpen

DOI:https://doi.org/10.1002/open.201402025· OSTI ID:1623577

Pratt, Lawrence M. ^[1]; Dixon, Darryl D. ^[2]; Tius, Marcus A. ^[2]

City Univ. of New York (CUNY), NY (United States); DOE/OSTI
Univ. of Hawaii at Manoa, Honolulu, HI (United States); Univ. of Hawaii Cancer Center, Honolulu, HI (United States)

A combined computational and ¹³C NMR study was used to investigate the formation of mixed aggregates of 1-methoxyallenyllithium and lithium chloride in tetrahydrofuran (THF) solution. The observed and calculated chemical shifts, as well as the calculated free energies of mixed aggregate formation (MP2/6-31+G(d)), are consistent with the formation of a mixed dimer as the major species in solution. Free energies of mixed dimer, trimer, and tetramer formation were calculated by using the B3LYP and MP2 methods and the 6-31+G(d) basis set. The two methods generated different predictions of which mixed aggregates will be formed, with B3LYP/6-31+ G(d) favoring mixed trimers and tetramers in THF solution, and MP2/6-31+G(d) favoring mixed dimers. Formation of the sterically unhindered mixed dimers is also consistent with the enhanced reactivity of these compounds in the presence of lithium chloride. The spectra are also consistent with some residual 1-methoxyallenyllithium tetramer, as well as small amounts of higher mixed aggregates. Although neither computational method is perfect, for this particular system, the calculated free energies derived using the MP2 method are in better agreement with experimental data than those derived using the B3LYP method.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE; National Science Foundation (NSF); National Institutes of Health (NIH)

Grant/Contract Number:: AC03-76SF00098

OSTI ID:: 1623577

Journal Information:: ChemistryOpen, Journal Name: ChemistryOpen Journal Issue: 6 Vol. 3; ISSN 2191-1363

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Asymmetric Cyclopentannelation: Camphor-Derived Auxiliary. Harrington, Paul E.; Murai, Tsuyoshi; Chu, Chester ChemInform, Vol. 34, Issue 6 https://doi.org/10.1002/chin.200306071	journal	February 2003
Cationic Cyclopentannelation of Allene Ethers Tius, Marcus A. Accounts of Chemical Research, Vol. 36, Issue 4 https://doi.org/10.1021/ar0200394	journal	April 2003
Synthesis and Absolute Stereochemistry of Roseophilin Harrington, Paul E.; Tius, Marcus A. Journal of the American Chemical Society, Vol. 123, Issue 35 https://doi.org/10.1021/ja011242h	journal	September 2001
A Computational Study of Lithium Enolate Mixed Aggregates Pratt, Lawrence M.; Streitwieser, Andrew The Journal of Organic Chemistry, Vol. 68, Issue 7 https://doi.org/10.1021/jo026902v	journal	April 2003
Structure, Bonding, and Solvation of Dilithiodiamines ^† Pratt, Lawrence M.; Mu, R. The Journal of Organic Chemistry, Vol. 69, Issue 22 https://doi.org/10.1021/jo048732n	journal	October 2004
Aggregation of Alkyllithiums in Tetrahydrofuran Pratt, Lawrence M.; Truhlar, Donald G.; Cramer, Christopher J. The Journal of Organic Chemistry, Vol. 72, Issue 8 https://doi.org/10.1021/jo062557o	journal	April 2007
Total Synthesis of (±)-Terpestacin and (±)-11- epi -Terpestacin Berger, Gideon O.; Tius, Marcus A. The Journal of Organic Chemistry, Vol. 72, Issue 17 https://doi.org/10.1021/jo070923d	journal	August 2007
A Computational Study of Lithium Ketone Enolate Aggregation in the Gas Phase and in THF Solution Pratt, Lawrence M.; Nguyen, Son C.; Thanh, Bui T. The Journal of Organic Chemistry, Vol. 73, Issue 16 https://doi.org/10.1021/jo800528y	journal	August 2008
Gas Phase and Solution Structures of 1-Methoxyallenyllithium Dixon, Darryl D.; Tius, Marcus A.; Pratt, Lawrence M. The Journal of Organic Chemistry, Vol. 74, Issue 16 https://doi.org/10.1021/jo9008063	journal	August 2009
Synthesis of 15-Deoxy-12-hydroxy-10-(trifluoromethyl)-Δ ⁷ -PGA ₁ Methyl Ester Tius, Marcus A.; Hu, Huaping; Kawakami, Joel K. The Journal of Organic Chemistry, Vol. 63, Issue 17 https://doi.org/10.1021/jo980621z	journal	August 1998
Asymmetric Cyclopentannelation. Chiral Auxiliary on the Allene Harrington, Paul E.; Tius, Marcus A. Organic Letters, Vol. 2, Issue 16 https://doi.org/10.1021/ol0001362	journal	August 2000
Synthesis of (+)-Madindoline A and (+)-Madindoline B Wan, Lifeng; Tius, Marcus A. Organic Letters, Vol. 9, Issue 4 https://doi.org/10.1021/ol062919e	journal	February 2007
Lewis Acid-Catalyzed Conjugate Additions of Silyloxyallenes: A Selective Solution to the Intermolecular Rauhut−Currier Problem Reynolds, Troy E.; Binkley, Michael S.; Scheidt, Karl A. Organic Letters, Vol. 10, Issue 12 https://doi.org/10.1021/ol800745q	journal	June 2008
A New Approach to Neuraminic Acid Analogues via 1,2-Oxazines Bressel, Bettina; Reissig, Hans-Ulrich Organic Letters, Vol. 11, Issue 3 https://doi.org/10.1021/ol802514m	journal	February 2009
Struktur und Reaktivität von Lithiumenolaten, vom Pinakolon zur selektivenC-Alkylierung von Peptiden – Schwierigkeiten und Möglichkeiten durch komplexe Strukturen Seebach, Dieter Angewandte Chemie, Vol. 100, Issue 12 https://doi.org/10.1002/ange.19881001206	journal	December 1988
Structure and Reactivity of Lithium Enolates. From Pinacolone to SelectiveC-Alkylations of Peptides. Difficulties and Opportunities Afforded by Complex Structures Seebach, Dieter Angewandte Chemie International Edition in English, Vol. 27, Issue 12 https://doi.org/10.1002/anie.198816241	journal	December 1988
Calculation of the solvation state of organolithium compounds: Effects of basis sets and electron correlation methods Pratt, Lawrence M.; Jones, Darrel; Sease, Andrea International Journal of Quantum Chemistry, Vol. 109, Issue 1 https://doi.org/10.1002/qua.21772	journal	January 2009
Synthesis of (±)-xanthocidin Tius, Marcus A.; Drake, David J. Tetrahedron, Vol. 52, Issue 47 https://doi.org/10.1016/0040-4020(96)00913-1	journal	November 1996
Préparation et utilisation de lithiens de mono- et disilanes alléniques fonctionnels Mantione, Richard; Leroux, Yves Journal of Organometallic Chemistry, Vol. 31, Issue 1 https://doi.org/10.1016/S0022-328X(00)87458-6	journal	August 1971
Silicon in synthesis: 1-trimethylsilyl-1-methoxy allene; a reagent for the direct conversion of aliphatic aldehydes into 2-trimethylsilyl furans Pappalardo, Paul; Ehlinger, Ed; Magnus, Philip Tetrahedron Letters, Vol. 23, Issue 3 https://doi.org/10.1016/S0040-4039(00)86817-3	journal	January 1982
A new stereoselective synthesis of -α, β- unsaturated carbonyl compounds. Clinet, Jean-Claude; Linstrumelle, Gerard Tetrahedron Letters, Vol. 21, Issue 41 https://doi.org/10.1016/S0040-4039(00)92851-X	journal	January 1980
An imino Nazarov cyclization Tius, Marcus A.; Chu, Chester C.; Nieves-Colberg, Raquel Tetrahedron Letters, Vol. 42, Issue 13 https://doi.org/10.1016/S0040-4039(01)00201-5	journal	March 2001
Cationic cyclopentannelation. Synthesis of (d,1)-xanthocidin Tius, Marcus A.; Astrab, Donald P. Tetrahedron Letters, Vol. 30, Issue 18 https://doi.org/10.1016/S0040-4039(01)80391-9	journal	January 1989
3-alcoxy-allenyllithium reagents as β-acyl vinyl anion equivalents. A new synthesis of pyrenophorin. Derguini, Fadila; Linstrumelle, Gérard Tetrahedron Letters, Vol. 25, Issue 50 https://doi.org/10.1016/S0040-4039(01)81680-4	journal	January 1984
A cationic cyclopentannelation Tius, Marcus A.; Astrab, Donald P. Tetrahedron Letters, Vol. 25, Issue 15 https://doi.org/10.1016/S0040-4039(01)90004-8	journal	January 1984
Metallation of propargylic and allenic ethers synthesis of α, β-unsaturated carbonyl compounds. Leroux, Yves; Roman, Chantal Tetrahedron Letters, Vol. 14, Issue 28 https://doi.org/10.1016/S0040-4039(01)96150-7	journal	January 1973
A new allenic dianion: selective mono and bialkylation. Leroux, Yves; Mantione, Richard Tetrahedron Letters, Vol. 12, Issue 7 https://doi.org/10.1016/S0040-4039(01)96504-9	journal	January 1971
Synthesis and reactions of lithium derivatives of mono and disilylated t-butoxyallenes. Mantione, Richard; Leroux, Yves Tetrahedron Letters, Vol. 12, Issue 7 https://doi.org/10.1016/S0040-4039(01)96505-0	journal	January 1971
A computational study of lithium methoxide mixed aggregates with alkyllithiums Pratt, Lawrence M.; Kwon, Ohyun; Ho, Thanh Chi Tetrahedron, Vol. 64, Issue 22 https://doi.org/10.1016/j.tet.2008.03.022	journal	May 2008
Modeling lithium dialkylamides in ethereal solvents: A test of the microsolvation model Pratt, Lawrence M. Journal of Molecular Structure: THEOCHEM, Vol. 811, Issue 1-3 https://doi.org/10.1016/j.theochem.2006.12.060	journal	June 2007
Cationic cyclopentaannelation: an efficient methylenomycin synthesis Tius, Marcus A.; Astrab, Donald P.; Fauq, Abdul H. Journal of the American Chemical Society, Vol. 108, Issue 12 https://doi.org/10.1021/ja00272a045	journal	June 1986
An unusual new allene cyclization reaction. Synthesis of dihydrofuran-3(2H)-ones Gange, David; Magnus, Philip Journal of the American Chemical Society, Vol. 100, Issue 24 https://doi.org/10.1021/ja00492a061	journal	November 1978
Silyl ketone chemistry. Preparation of siloxyallenyl- and -allyllithium reagents Reich, Hans J.; Olson, Richard E.; Clark, Mark C. Journal of the American Chemical Society, Vol. 102, Issue 4 https://doi.org/10.1021/ja00524a036	journal	February 1980
Asymmetric Cyclopentannelation: Camphor-Derived Auxiliary Harrington, Paul E.; Murai, Tsuyoshi; Chu, Chester Journal of the American Chemical Society, Vol. 124, Issue 34 https://doi.org/10.1021/ja020591o	journal	August 2002
Effect of Temperature and Pressure on the Volumetric Properties of Branched and Cyclic Ethers Govender, U. P.; Letcher, T. M.; Garg, S. K. Journal of Chemical & Engineering Data, Vol. 41, Issue 1 https://doi.org/10.1021/je9501494	journal	January 1996
Selective mono- and polymethylene homologations of copper reagents using (iodomethyl)zinc iodide Sidduri, AchyuthaRao; Rozema, Michael J.; Knochel, Paul The Journal of Organic Chemistry, Vol. 58, Issue 10 https://doi.org/10.1021/jo00062a010	journal	May 1993
A concise synthesis of d,l-methylenomycin A and d,l-epi-methylenomycin A Tius, Marcus A.; Trehan, Sanjay The Journal of Organic Chemistry, Vol. 54, Issue 1 https://doi.org/10.1021/jo00262a017	journal	January 1989
Solvent Effects on the Aggregation State of Lithium Dialkylaminoborohydrides Pratt, Lawrence M.; Mogali, Sudha; Glinton, Kevin The Journal of Organic Chemistry, Vol. 68, Issue 17 https://doi.org/10.1021/jo034498+	journal	July 2003
Structure, Bonding, and Solvation of Lithium Vinylcarbenoids Pratt, Lawrence M.; Nguỹên, Ngân Vǎn; Lê, Lý Th. i. The Journal of Organic Chemistry, Vol. 70, Issue 6 https://doi.org/10.1021/jo048143h	journal	March 2005
Computational Strategies for Evaluating Barrier Heights for Gas-Phase Reactions of Lithium Enolates Pratt, Lawrence M.; Vǎn Nguỹên, Ngân; Ramachandran, B. The Journal of Organic Chemistry, Vol. 70, Issue 11 https://doi.org/10.1021/jo0503409	journal	May 2005
Traceless Chiral Auxiliaries for the Allene Ether Nazarov Cyclization Banaag, April R.; Tius, Marcus A. The Journal of Organic Chemistry, Vol. 73, Issue 21 https://doi.org/10.1021/jo801503c	journal	November 2008
Novel Diborane-Analogue Transition Structures for Borane Reactions with Alkyl Halides ^† Pratt, Lawrence M.; Vǎn Nguỹên, Ngân The Journal of Physical Chemistry A, Vol. 110, Issue 2 https://doi.org/10.1021/jp054057p	journal	January 2006
Scope of a Novel Three-Component Synthesis of Highly Functionalized Pyridines ^† Dash, Jyotirmayee; Lechel, Tilman; Reissig, Hans-Ulrich Organic Letters, Vol. 9, Issue 26 https://doi.org/10.1021/ol702468s	journal	December 2007
Hydroxyquinone annelation Tius, Marcus A.; Cullingham, Jean M.; Ali, S. Journal of the Chemical Society, Chemical Communications, Issue 13 https://doi.org/10.1039/c39890000867	journal	January 1989
Alkoxyallenes - Building Blocks in Organic Synthesis Zimmer, Reinhold Synthesis, Vol. 1993, Issue 02 https://doi.org/10.1055/s-1993-25823	journal	January 1993
Predicting aqueous solubilities from aqueous free energies of solvation and experimental or calculated vapor pressures of pure substances Thompson, Jason D.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Chemical Physics, Vol. 119, Issue 3 https://doi.org/10.1063/1.1579474	journal	July 2003
A Computational Study of Lithium Dialkylamide Mixed Aggregates with Lithium Chloride Pratt, Lawrence M. Bulletin of the Chemical Society of Japan, Vol. 78, Issue 5 https://doi.org/10.1246/bcsj.78.890	journal	May 2005
Basis Set and Electron Correlation Effects on Lithium Carbenoid Dimerization Energies Pratt, Lawrence M.; Phan, Diep Huong Tran; Tran, Phuong Thao Thi Bulletin of the Chemical Society of Japan, Vol. 80, Issue 8 https://doi.org/10.1246/bcsj.80.1587	journal	August 2007