2,2,2-Trichloroethyl Aryldiazoacetates as Robust Reagents for the Enantioselective C-H Functionalization of Methyl Ethers.
Guptill, David M.; Davies, Huw M. L.; Journal of the American Chemical Society  (2014) 141215145223006–; doi:10.1021/ja5107404

data_4123143
_publ_section_title
;
 2,2,2-Trichloroethyl Aryldiazoacetates as Robust Reagents for the
 Enantioselective C-H Functionalization of Methyl Ethers.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141215145223006
_journal_paper_doi               10.1021/ja5107404
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         '0.5(C13 H16 Br O3), 0.5(C13 H17 Br O3)'
_chemical_formula_sum            'C13 H16.5 Br O3'
_chemical_formula_weight         300.67
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2014-08-20
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   5.460(2)
_cell_length_b                   19.858(7)
_cell_length_c                   25.535(10)
_cell_measurement_reflns_used    5247
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      25.103
_cell_measurement_theta_min      3.235
_cell_volume                     2768.6(18)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2014.1-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      110(2)
_diffrn_detector_area_resol_mean 512
_diffrn_measured_fraction_theta_full 0.811
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2262
_diffrn_reflns_av_unetI/netI     0.2834
_diffrn_reflns_Laue_measured_fraction_full 0.811
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            10242
_diffrn_reflns_point_group_measured_fraction_full 0.802
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         23.533
_diffrn_reflns_theta_min         1.896
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.964
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.3191
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/2 (Bruker,2014) was used for absorption correction.
wR2(int) was 0.1258 before and 0.0796 after correction.
The Ratio of minimum to maximum transmission is 0.4281.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_description       needle
_exptl_crystal_F_000             1228
_exptl_crystal_size_max          1.443
_exptl_crystal_size_mid          0.054
_exptl_crystal_size_min          0.033
_refine_diff_density_max         1.925
_refine_diff_density_min         -1.806
_refine_diff_density_rms         0.271
_refine_ls_abs_structure_details
;
 Flack x determined using 472 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.03(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         4028
_refine_ls_number_restraints     257
_refine_ls_restrained_S_all      0.981
_refine_ls_R_factor_all          0.1946
_refine_ls_R_factor_gt           0.0886
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1241P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1995
_refine_ls_wR_factor_ref         0.2831
_reflns_Friedel_coverage         0.700
_reflns_Friedel_fraction_full    0.790
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                2045
_reflns_number_total             4028
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5107404_si_002.cif
_cod_data_source_block           dmg26-old
_cod_original_formula_sum        'C13 H16.50 Br O3'
_cod_database_code               4123143
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.909
_shelx_estimated_absorpt_t_min   0.100
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O2'-H3
 1.695 with sigma of 0.001
 H3-O3
 0.959 with sigma of 0.001
 O3'-H3'
 0.975 with sigma of 0.002
 O2_$1-H3'
 1.695 with sigma of 0.002
3. Rigid bond restraints
 C3', C2'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C3) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C5') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C3') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C1') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C6') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O2') \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C8') \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C4') \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C9') \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(Br1') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C4) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O1) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C9) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C8) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C5) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C13') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C13') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(O3') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C1') = Uanis(C4')
Uanis(C7) = Uanis(C13)
Uanis(C2) = Uanis(C3)
Uanis(C4) = Uanis(C1)
Uanis(C5) = Uanis(C6)
Uanis(C13') = Uanis(C7')
5. Rigid body (RIGU) restrains
 Br1, C1
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C1, C2, C6
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C7, C13
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C7, C8
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C8, O1
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O1, C9, C11, C12, C10
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C1', Br1'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C5', C6'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C8', O1', C7'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O1', C9', C12', C11', C10'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C5', C4'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4', C3'
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4', C7'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C5, C4, C3
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4, C7
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C7', C13'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O3, C13, O2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O3', C13', O2'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6.a Ternary CH refined with riding coordinates:
 C7(H7), C7'(H7')
6.b Secondary CH2 refined with riding coordinates:
 C8'(H8'A,H8'B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3A), C5(H5), C2(H2), C8(H8), C6(H6), C6'(H6'), C3'(H3'A), C5'(H5'),
 C2'(H2')
6.d Idealised Me refined as rotating group:
 C12(H12D,H12E,H12F), C11(H11D,H11E,H11F), C10(H10D,H10E,H10F), C12'(H12A,H12B,
 H12C), C10'(H10A,H10B,H10C), C11'(H11A,H11B,H11C)
;
_olex2_submission_original_sample_id dmg26-061
_olex2_submission_special_instructions 'No special instructions were received'