Stereoselective synthesis of 1-substituted organometallic derivatives of 3,3-dimethylbutane-1,2-d2

Bock, Paul L.; Whitesides, George M.

doi:10.1021/ja00816a026

Cited by 56 publications

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“…This is verified by empirical measures of nucleophilicity that CN À has a larger nucleophilic constant 59 at 6.7 than OH À at 6.5. [60][61][62] Our results also show that the presence of water solution increases the activation barrier height by 16.2 kcal mol À1 for CH 3 Br + OH À ; however, it increases only to 14.5 kcal mol À1 for CH 3 Br + CN À . This is expected since OH À has a larger hardness parameter at 5.6 than CN À at 5.3; 63 in other words, the OH À anion has a more localized charge than CN À .…”

Section: Solution Contributionsupporting

confidence: 58%

Solvent effects and potential of mean force: a multilayered-representation quantum mechanical/molecular mechanics study of the CH₃Br + CN⁻ reaction in aqueous solution

Zhang

Wang

2014

Phys. Chem. Chem. Phys.

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The bimolecular nucleophilic substitution (SN2) reaction of CH3Br and CN(-) in aqueous solution was investigated using a multilayered-representation quantum mechanical and molecular mechanics methodology. The reactant complex, transition state, and product complex are identified and characterized in aqueous solution. The potentials of mean force are computed at both DFT and CCSD(T) levels of theory for the reaction region. The CCSD(T)/MM level of theory presents a free energy activation barrier height at 19.1 kcal mol(-1) which agrees very well with the experimental value of 20.7 kcal mol(-1), while the DFT/MM level of theory underestimated the barrier height at 16.5 kcal mol(-1). The results show that the aqueous environment has a significant contribution to the potential of mean force. Both the solvation effect and the polarization effect increase the activation barrier height by ∼14.5 kcal mol(-1) and the solvation effect plays a major role by providing about 70% of the contribution.

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Section: Solution Contributionsupporting

confidence: 58%

Solvent effects and potential of mean force: a multilayered-representation quantum mechanical/molecular mechanics study of the CH₃Br + CN⁻ reaction in aqueous solution

Zhang

Wang

2014

Phys. Chem. Chem. Phys.

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“…1: IR (film) 2070,3040,2930,2830,1490,1455,1380,1120, 750, 695 cm-* 1; NMR (CDC1S) 1.74 (m, 3 ), 2.20 (m, 4 H), 4.34 (m, 2 H), 4.55 (dd, J = 5, 9 Hz), 5.52 (m, 1 ), 7.40 (s, 5 H).…”

mentioning

confidence: 99%

“…The boiling point [105-107 °C (15 mmHg)] was identical with the literature13 boiling point. 3 (R = CN): mp 75-76 °C; IR (film) 2980, 2880, 2205,1120 cm"1; 100-MHz NMR (CDC13) 0.10 (s, 6 ), 0.91 (s, 9 ), 1.72 (br s, 3 ), 1.8-2.0 (m, 4 ), 2.07 (t,J=2 Hz, 3 H), 3.57, 3.70 (AB q, J = 10 Hz, 2 ), 4.15 (m, 3 H), 5.44 (m, 1 H); high-resolution mass spectrum for Ci5H2202NSI (P -57) requires m/e 276.15103, found m/e 276.14199. 4 (R = SPh): IR (film) 3035, 2970, 2940, 2870,1685,1480,1445, 1260,1105,1070, 740, 690 cm"1; 100-MHz NMR (CDC13) 0.06 (s, 6 ), 0.92 (s, 9 ), 1.75 (m, 3 ), 1.90 (m, 4 ), 1.97 (t, 3 H, J = 2 Hz), 3.60 and 3.80 (AB q, 2 H, J = 10 Hz), 4.07 (m, 2 H), 4.30 (m, 1 H), 5.47 (m, 1 H).…”

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confidence: 99%

“…( 3) Representative examples include the following, (a) Tetraisopropyldisoloxane: Markiewiez, W. T. J. Chem. (k) Dimethylsilylene: Kelly, R. W. Tetrahedron Lett.…”

mentioning

confidence: 99%

“…H); mass spectrum for C^H^O,, requires m/e 240.1361, found m/e 240.1369.8 (R = H): NMR (CDC13)1.31 (s, 3 ),1.44 (m, 2 ), 1.80-2.48 (envelope, 7 H), 2.98 (m, 1 ),3.40 (m, 3 H),3.74 (m, 3 ),4.60 (s, 2 H), 7.34 (s, 5 H); 13C NMR (CDC13) 21.718, 22.433, 29.003,…”

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confidence: 99%

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p-Methoxyacetophenone dimethyl ketal and .alpha.,p-dimethoxystyrene. Efficient and useful reagents for 1,2- and 1,3-diol protection

Lipshutz¹,

Morey²

1981

J. Org. Chem.

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2419General Procedure. Diisobutylaluminum hydride (1.0 M, hexanes) was added portionwise to a 0.3 M toluene solution of the unsaturated lactone (7.0 mmol) cooled to -78 O C (dry ice-CH30H bath) until TLC analysis judged the reaction complete.It was then poured into a rapidly stirred mixture of ice (25 g) and acetic acid (7 mL). Chloroform (50 mL) was added and the twephase system stirred vigorously for 10 min. Another 100-mL portion of chloroform was added and vigorous stirring continued until two distinct layers formed when the stirring was halted (typically 3 0 4 min). The layers were separated, and the organic layer was washed with bicarbonate (2 X 100 mL) and brine (75 mL). Drying and removal of the solvents afforded a colorless oil which was used without purification.The crude lactol and triethylsilane (1.22 g, 10.5 mmol) in dichloromethane (25 mL) were cooled under nitrogen. Dropwise addition of boron trifluoride etherate (0.95 mL, 7.7 mmol) gave a solution which was stirred until TLC indicated that no lactol was present and then quenched by addition of ca. 10 mL of aqueous bicarbonate. The cooling bath was removed and the solution allowed to warm to room temperature with vigorous stirring. After the mixture was transferred to a separatory funnel, ether (100 mL) was added and the whole washed with bicarbonate (20 mL) and brine (20 mL). Drying and removal of the solvents afforded an oil which was chromatographed (silica gel, hexanes-EtOAc). 695 cm-'; NMR (CDClJ 6 1.74 (m, 3 H), 2.20 (m, 4 H), 4.34 (m, 2 H), 4.55 (dd, J = 5, 9 Hz), 5.52 (m, 1 H), 7.40 (s, 5 H).2: IR (film) 2980,2895, 1065; NMR (CDClJ 6 1.52-2.42 (m, 4 H), 3.704.18 (m, 2 H), 4.68-4.94 (m, 1 H), 7.03-7.30 (m, 5 H); ' % NMR 143.315,128.146,126.954, 125.492,80.527,68.446,34.534, 25.919. The boiling point [105-107 "C (15 mmHg)] was identical with the literature13 boiling point.

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From Metal Salts

Wardell¹

1988

Inorganic Reactions and Methods

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Stereoselective synthesis of 1-substituted organometallic derivatives of 3,3-dimethylbutane-1,2-d2

Cited by 56 publications

References 1 publication

Solvent effects and potential of mean force: a multilayered-representation quantum mechanical/molecular mechanics study of the CH₃Br + CN⁻ reaction in aqueous solution

Solvent effects and potential of mean force: a multilayered-representation quantum mechanical/molecular mechanics study of the CH₃Br + CN⁻ reaction in aqueous solution

p-Methoxyacetophenone dimethyl ketal and .alpha.,p-dimethoxystyrene. Efficient and useful reagents for 1,2- and 1,3-diol protection

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Stereoselective synthesis of 1-substituted organometallic derivatives of 3,3-dimethylbutane-1,2-d2

Cited by 56 publications

References 1 publication

Solvent effects and potential of mean force: a multilayered-representation quantum mechanical/molecular mechanics study of the CH3Br + CN− reaction in aqueous solution

Solvent effects and potential of mean force: a multilayered-representation quantum mechanical/molecular mechanics study of the CH3Br + CN− reaction in aqueous solution

p-Methoxyacetophenone dimethyl ketal and .alpha.,p-dimethoxystyrene. Efficient and useful reagents for 1,2- and 1,3-diol protection

From Metal Salts

Contact Info

Product

Resources

About

Solvent effects and potential of mean force: a multilayered-representation quantum mechanical/molecular mechanics study of the CH₃Br + CN⁻ reaction in aqueous solution

Solvent effects and potential of mean force: a multilayered-representation quantum mechanical/molecular mechanics study of the CH₃Br + CN⁻ reaction in aqueous solution