Ammonium-Directed Olefinic Epoxidation: Kinetic and Mechanistic Insights
Méabh B. Brennan; Timothy D. W. Claridge; Richard G. Compton; Stephen G. Davies; Ai M. Fletcher; Martin C. Henstridge; David S. Hewings; Wataru Kurosawa; James A. Lee; Paul M. Roberts; Anne K. Schoonen; James E. Thomson; Journal of Organic Chemistry 77 (2012) 7241–7261; doi:10.1021/jo3010556

data_4027429
_publ_contact_author             'Stephen G. Davies'
_publ_contact_author_email       steve.davies@chem.ox.ac.uk
_publ_contact_author_fax         '+44 1865 275633'
_publ_contact_author_phone       '+44 1865 275695'
_publ_section_title
;
 Ammonium-Directed Olefinic Epoxidation: Kinetic and Mechanistic Insights
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              7241
_journal_page_last               7261
_journal_paper_doi               10.1021/jo3010556
_journal_volume                  77
_journal_year                    2012
_chemical_formula_moiety         'C16 H20 Cl3 N1 O3'
_chemical_formula_sum            'C16 H20 Cl3 N O3'
_chemical_formula_weight         380.70
_space_group_IT_number           14
_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 118.5948(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.2170(3)
_cell_length_b                   11.5367(3)
_cell_length_c                   18.8611(4)
_cell_measurement_reflns_used    7075
_cell_measurement_temperature    150
_cell_measurement_theta_max      27
_cell_measurement_theta_min      5
_cell_volume                     3480.43(14)
_computing_cell_refinement       'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 1997-2001).'
_computing_data_reduction        'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'CAMERON (Watkin et al., 1996)'
_computing_publication_material  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_refinement  'CRYSTALS (Betteridge et al., 2003)'
_computing_structure_solution    'SIR92 (Altomare et al., 1994)'
_diffrn_ambient_temperature      150
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_device       'Nonius KappaCCD'
_diffrn_measurement_device_type  Area
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.027
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            13710
_diffrn_reflns_theta_full        26.108
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         5.099
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.540
_exptl_absorpt_correction_T_max  0.90
_exptl_absorpt_correction_T_min  0.90
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'DENZO/SCALEPACK (Otwinowski & Minor, 1997)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.453
_exptl_crystal_description       plate
_exptl_crystal_F_000             1584
_exptl_crystal_size_max          0.30
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.20
_refine_diff_density_max         1.01
_refine_diff_density_min         -0.52
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.1169
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     415
_refine_ls_number_reflns         5496
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0754
_refine_ls_R_factor_gt           0.0525
_refine_ls_shift/su_max          0.000502
_refine_ls_structure_factor_coef F
_refine_ls_weighting_details
;
Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982)
[weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)]
where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax
Method = Robust Weighting (Prince, 1982)
W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^
A~i~ are:
1.06 0.556 0.633
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_all         0.0729
_refine_ls_wR_factor_gt          0.0554
_refine_ls_wR_factor_ref         0.0527
_reflns_limit_h_max              20
_reflns_limit_h_min              -23
_reflns_limit_k_max              14
_reflns_limit_k_min              0
_reflns_limit_l_max              24
_reflns_limit_l_min              0
_reflns_number_gt                6016
_reflns_number_total             7877
_reflns_threshold_expression     I>2.0\s(I)
_oxford_diffrn_Wilson_B_factor   2.55
_oxford_diffrn_Wilson_scale      7.58
_oxford_refine_ls_r_factor_ref   0.0472
_oxford_refine_ls_scale          0.3710(6)
_oxford_reflns_number_all        7877
_oxford_reflns_threshold_expression_ref I>3.0\s(I)
_cod_data_source_file            jo3010556_si_001_2.cif
_cod_data_source_block           14
_cod_original_formula_sum        'C16 H20 Cl3 N1 O3'
_cod_database_code               4027429