Diastereoselective Synthesis of P-Stereogenic Secondary Phosphine Oxides (SPOs) Bearing a Chiral Substituent by Ring Opening of (+)-Limonene Oxide with Primary Phosphido Nucleophiles.
Zimmerman, Amber; Xu, Rebecca; Reynolds, Samantha C.; Shipp, Chase; Marshall, Derrick; Wang, Ge; Blank, Natalia F.; Gibbons, Sarah; Hughes, Russell P.; Glueck, David S.; Balaich, Gary James; Rheingold, Arnold L.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00974

data_4038583
_publ_section_title
;
 Diastereoselective Synthesis of P-Stereogenic Secondary Phosphine Oxides
 (SPOs) Bearing a Chiral Substituent by Ring Opening of (+)-Limonene Oxide
 with Primary Phosphido Nucleophiles.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00974
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C16 H23 O2 P'
_chemical_formula_sum            'C16 H23 O2 P'
_chemical_formula_weight         278.31
_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'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-11-13
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.9884(2)
_cell_length_b                   13.6655(5)
_cell_length_c                   18.8441(7)
_cell_measurement_reflns_used    9834
_cell_measurement_temperature    100
_cell_measurement_theta_max      72.06
_cell_measurement_theta_min      4.00
_cell_volume                     1542.10(10)
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0793
_diffrn_reflns_av_unetI/netI     0.0347
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            20713
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.243
_diffrn_reflns_theta_min         3.996
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.541
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.909
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.199
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.27
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.372
_refine_diff_density_min         -0.213
_refine_diff_density_rms         0.038
_refine_ls_abs_structure_details
;
 Flack x determined using 1182 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.013(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     190
_refine_ls_number_reflns         3055
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0318
_refine_ls_R_factor_gt           0.0301
_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^)+(0.0399P)^2^+0.3161P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0760
_refine_ls_wR_factor_ref         0.0774
_reflns_Friedel_coverage         0.708
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                2941
_reflns_number_total             3055
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00974_si_003.cif
_cod_data_source_block           glu544_0m_a
_cod_database_code               4038583
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.887
_shelx_estimated_absorpt_t_min   0.681
_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.a Ternary CH refined with riding coordinates:
 C7(H7), C9(H9)
2.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C8(H8A,H8B), C11(H11A,H11B)
2.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C1(H1B), C3(H3), C2(H2), C4(H4)
2.d Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C15(H15A,H15B,H15C)
;
_shelx_res_checksum              19562
_shelx_hkl_checksum              52346
_olex2_submission_special_instructions 'No special instructions were received'