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_4038586
_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         'C28 H47 O2 P'
_chemical_formula_sum            'C28 H47 O2 P'
_chemical_formula_weight         446.62
_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             2020-02-06
_audit_creation_method
;
Olex2 1.2
(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            12
_cell_length_a                   12.164(6)
_cell_length_b                   17.590(8)
_cell_length_c                   38.736(19)
_cell_measurement_reflns_used    785
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      21.77
_cell_measurement_theta_min      6.08
_cell_volume                     8288(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 v2013.6-2 (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      150.0
_diffrn_detector_area_resol_mean 8.0
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_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  0.0700
_diffrn_reflns_av_unetI/netI     0.0959
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -46
_diffrn_reflns_number            38857
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.305
_diffrn_reflns_theta_min         1.051
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.120
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.7081
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0611 before and 0.0588 after correction.
The Ratio of minimum to maximum transmission is 0.9502.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.074
_exptl_crystal_description       block
_exptl_crystal_F_000             2952
_exptl_crystal_size_max          0.45
_exptl_crystal_size_mid          0.42
_exptl_crystal_size_min          0.38
_refine_diff_density_max         0.406
_refine_diff_density_min         -0.235
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 3288 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.08(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.005
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     886
_refine_ls_number_reflns         15036
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.1022
_refine_ls_R_factor_gt           0.0614
_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^)+(0.0502P)^2^+1.1288P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1149
_refine_ls_wR_factor_ref         0.1322
_reflns_Friedel_coverage         0.813
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                10388
_reflns_number_total             15036
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00974_si_003.cif
_cod_data_source_block           glu545_0m_a
_cod_database_code               4038586
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.948
_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.a Ternary CH refined with riding coordinates:
 C1"(H1"A), C1'(H1'A), C1(H1A), C3"(H3"), C3(H3), C3'(H3')
2.b Secondary CH2 refined with riding coordinates:
 C5"(H5"A,H5"B), C2'(H2'A,H2'B), C2"(H2"A,H2"B), C2(H2A,H2B), C5'(H5'A,H5'B),
 C5(H5A,H5B), C4'(H4'A,H4'B), C4(H4A,H4B), C4"(H4"A,H4"B)
2.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C13"(H13"), C13'(H13'), C15(H15), C15"(H15"), C15'(H15')
2.d X=CH2 refined with riding coordinates:
 C8(H8A,H8B), C8'(H8'A,H8'B), C8"(H8"A,H8"B)
2.e Idealised Me refined as rotating group:
 C26(H26D,H26E,H26F), C27'(H27G,H27H,H27I), C28'(H28G,H28H,H28I), C26"(H26A,
 H26B,H26C), C27(H27D,H27E,H27F), C10"(H10A,H10B,H10C), C27"(H27A,H27B,H27C),
 C23(H23D,H23E,H23F), C22(H22D,H22E,H22F), C26'(H26G,H26H,H26I), C24"(H24A,H24B,
 H24C), C28(H28D,H28E,H28F), C10(H10D,H10E,H10F), C18(H18D,H18E,H18F), C20(H20D,
 H20E,H20F), C19(H19D,H19E,H19F), C28"(H28A,H28B,H28C), C24(H24D,H24E,H24F),
 C9(H9A,H9B,H9C), C22"(H22A,H22B,H22C), C10'(H10G,H10H,H10I), C23"(H23A,H23B,
 H23C), C18'(H18G,H18H,H18I), C20"(H20A,H20B,H20C), C9'(H9'A,H9'B,H9'C),
 C19"(H19A,H19B,H19C), C23'(H23G,H23H,H23I), C19'(H19G,H19H,H19I), C22'(H22G,
 H22H,H22I), C18"(H18A,H18B,H18C), C20'(H20G,H20H,H20I), C24'(H24G,H24H,H24I),
 C9"(H9"A,H9"B,H9"C)
2.f Idealised tetrahedral OH refined as rotating group:
 O2"(H2"), O2(H2), O2'(H2')
;
_shelx_res_checksum              88547
_shelx_hkl_checksum              25048
_olex2_submission_special_instructions 'No special instructions were received'