Utility of Bifunctional N-Heterocyclic Phosphine (NHP)-Thioureas for Metal-Free Carbon-Phosphorus Bond Construction toward Regio- and Stereoselective Formation of Vinylphosphonates.
Mulla, Karimulla; Aleshire, Kyle L.; Forster, Paul M.; Kang, Jun Yong; The Journal of organic chemistry 81 (2016) 77–88; doi:10.1021/acs.joc.5b02184

data_4036481
_publ_section_title
;
 Utility of Bifunctional N-Heterocyclic Phosphine (NHP)-Thioureas for
 Metal-Free Carbon-Phosphorus Bond Construction toward Regio- and
 Stereoselective Formation of Vinylphosphonates.
;
_journal_issue                   1
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              77
_journal_page_last               88
_journal_paper_doi               10.1021/acs.joc.5b02184
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety         'C20 H23 N2 O3 P'
_chemical_formula_sum            'C20 H23 N2 O3 P'
_chemical_formula_weight         370.37
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-06-05
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.5763(9)
_cell_length_b                   9.7340(5)
_cell_length_c                   19.8284(10)
_cell_measurement_reflns_used    8906
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.45
_cell_measurement_theta_min      2.19
_cell_volume                     3585.4(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      99.91
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0483
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            41586
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.368
_diffrn_reflns_theta_min         2.054
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.177
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.7217
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0586 before and 0.0557 after correction.
The Ratio of minimum to maximum transmission is 0.9673.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.372
_exptl_crystal_description       plate
_exptl_crystal_F_000             1568
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.324
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     244
_refine_ls_number_reflns         3628
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.0388
_refine_ls_R_factor_gt           0.0298
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0479P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0768
_refine_ls_wR_factor_ref         0.0807
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2931
_reflns_number_total             3628
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo5b02184_si_003.cif
_cod_data_source_block           kang3c_0ma_a_a
_cod_database_code               4036481
_shelxl_version_number           2014/6
_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
2. Uiso/Uaniso restraints and constraints
Uanis(O1) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
3.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C17(H17A,H17B), C19(H19A,H19B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14)
3.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_olex2_submission_special_instructions 'No special instructions were received'