Oxidative α-Trichloromethylation of Tertiary Amines: An Entry to α-Amino Acid Esters.
Xu, Changming; Zhu, Zhaobin; Wang, Yongchang; Jing, Zhiguo; Gao, Bin; Zhao, Li; Dong, Wen-Kui; The Journal of organic chemistry 84 (2019) 2234–2242; doi:10.1021/acs.joc.8b03238

data_4033792
_publ_section_title
;
 Oxidative \a-Trichloromethylation of Tertiary Amines: An Entry to
 \a-Amino Acid Esters.
;
_journal_issue                   4
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2234
_journal_page_last               2242
_journal_paper_doi               10.1021/acs.joc.8b03238
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C17 H16 Cl3 N'
_chemical_formula_sum            'C17 H16 Cl3 N'
_chemical_formula_weight         340.66
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-12-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.7690(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.8286(2)
_cell_length_b                   17.7357(5)
_cell_length_c                   15.3923(5)
_cell_measurement_reflns_used    9849
_cell_measurement_temperature    291(2)
_cell_measurement_theta_max      66.64
_cell_measurement_theta_min      3.80
_cell_volume                     1590.41(9)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS-1997 (Sheldrick, 2008)'
_diffrn_ambient_temperature      291.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0825
_diffrn_reflns_av_unetI/netI     0.0455
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            23492
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.829
_diffrn_reflns_theta_max         66.829
_diffrn_reflns_theta_min         3.803
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    5.139
_exptl_absorpt_correction_type   none
_exptl_crystal_density_diffrn    1.423
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.26
_refine_diff_density_max         0.694
_refine_diff_density_min         -1.064
_refine_diff_density_rms         0.161
_refine_ls_extinction_coef       0.092(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     218
_refine_ls_number_reflns         2806
_refine_ls_number_restraints     141
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0715
_refine_ls_R_factor_gt           0.0695
_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^)+(0.1348P)^2^+0.4322P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1726
_refine_ls_wR_factor_ref         0.1765
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2623
_reflns_number_total             2806
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b03238_si_002.cif
_cod_data_source_block           cu_20180911a_0m
_cod_database_code               4033792
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.348
_shelx_estimated_absorpt_t_min   0.308
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Rigid bond restraints
 Cl1A, Cl2A, Cl3A, Cl2B, Cl3B, Cl1B, C17
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
3. Uiso/Uaniso restraints and constraints
Cl1A \\sim Cl2A \\sim Cl3A \\sim Cl2B \\sim Cl3B \\sim Cl1B \\sim C17: within
3.8A with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Same fragment restrains
{Cl1A, Cl2A, Cl3A} sigma for 1-2: 0.02, 1-3: 0.04
as
{Cl2B, Cl3B, Cl1B}
5. Others
 Fixed Sof: Cl1A(0.5) Cl2A(0.5) Cl3A(0.5) Cl2B(0.5) Cl3B(0.5) Cl1B(0.5)
6.a Ternary CH refined with riding coordinates:
 C16(H16)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C8(H8A,H8B), C9(H9A,H9B)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14)
;
_shelx_res_checksum              41656
_shelx_hkl_checksum              41877
_olex2_submission_special_instructions 'No special instructions were received'