Scalable Synthesis of Enantiopure Bis-3,4-diazaphospholane Ligands for Asymmetric Catalysis.
Jones, Bradley R.; Abrams, M. Leigh; Landis, Clark R.; May, Scott A.; Campbell, Alison N.; Martinelli, Joseph R.; Calvin, Joel R.; The Journal of organic chemistry 81 (2016) 11965–11970; doi:10.1021/acs.joc.6b01915

data_4037284
_publ_section_title
;
 Scalable Synthesis of Enantiopure Bis-3,4-diazaphospholane Ligands for
 Asymmetric Catalysis.
;
_journal_issue                   23
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11965
_journal_page_last               11970
_journal_paper_doi               10.1021/acs.joc.6b01915
_journal_volume                  81
_journal_year                    2016
_chemical_formula_moiety
'C46 H32 N4 O12 P2, 3.5(C10 H16 N O), 0.25(C20 H32 N2 O2.52), 8.06(O)'
_chemical_formula_sum            'C86 H96 N8 O24.21 P2'
_chemical_formula_weight         1690.99
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-06-12
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.05.21 svn.r2940 for OlexSys, GUI svn.r4846)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.2424(6)
_cell_length_b                   19.6060(7)
_cell_length_c                   50.4378(16)
_cell_measurement_reflns_used    9813
_cell_measurement_temperature    100
_cell_measurement_theta_min      2.418
_cell_volume                     19028.5(11)
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker-AXS, 2013)'
_computing_data_collection       'APEX2 Ver. 2013.12-0 (Bruker-AXS, 2013)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker-AXS, 2013)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008-2013)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008-2013)'
_computing_structure_refinement  'SHELXTL (Sheldrick, 2008-2013)'
_computing_structure_solution    'SHELXTL (Sheldrick, 2008-2013)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 10.24
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_device       '4-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE diffractometer'
_diffrn_measurement_method       '0.2\ \w and 0.2\ \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  'multilayer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0325
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       61
_diffrn_reflns_limit_l_min       -61
_diffrn_reflns_number            127871
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         72.655
_diffrn_reflns_theta_min         2.418
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms HB'
_exptl_absorpt_coefficient_mu    1.022
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6620
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0851 before and 0.0554 after correction.
The Ratio of minimum to maximum transmission is 0.8785.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             7133
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.202
_refine_diff_density_min         -0.850
_refine_diff_density_rms         0.154
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.03(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1550
_refine_ls_number_reflns         35688
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.1688
_refine_ls_R_factor_gt           0.1501
_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^)+(0.4500P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4166
_refine_ls_wR_factor_ref         0.4728
_reflns_Friedel_coverage         0.868
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                27586
_reflns_number_total             35688
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b01915_si_001.cif
_cod_data_source_block           landis48
_cod_database_code               4037284
_shelxl_version_number           2014-2
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.685
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C54A-C55A
 1.54 with sigma of 0.02
 C20-O5 \\sim C20-O6 \\sim C20-O5C \\sim C20-O6C \\sim C20A-O5A \\sim C20A-O6A
\\sim C20A-O5B \\sim C20A-O6B
 with sigma of 0.002
 O5-O6 \\sim O5C-O6C \\sim O5B-O6B \\sim O5A-O6A
 with sigma of 0.004
3. Uiso/Uaniso restraints and constraints
Uiso(C52F) = Uiso(C47F) = Uiso(C48F) = Uiso(C50F) = Uiso(C51F) = Uiso(C49F)
Uanis(C51B) = Uanis(C52B) = Uanis(C48B) = Uanis(C49B) = Uanis(C47B) =
Uanis(C50B)
Uiso(C52D) = Uiso(C51D) = Uiso(C50D) = Uiso(C48D) = Uiso(C49D) = Uiso(C47D)
Uiso(C47A) = Uiso(C48A) = Uiso(C49A) = Uiso(C50A) = Uiso(C51A) = Uiso(C52A)
4. Same fragment restrains
{P2, N3, C27, O7C, O8C, C28C, C29C, C30C, C31C, C32C, C33C, C34C}
as
{P2, N3, C27, O7, O8, C28, C29, C30, C31, C32, C33, C34}
{P2A, N3A, C27A, O7B, O8B, C28B, C29B, C30B, C31B, C32B, C33B, C34B}
as
{P2A, N3A, C27A, O7A, O8A, C28A, C29A, C30A, C31A, C32A, C33A, C34A}
5. Others
 Uiso(O14)=Uiso(O15)=Uiso(O16)=Uiso(O17)=Uiso(O18)=Uiso(O19)=Uiso(O20)=
 Uiso(O21)=Uiso(O22)=Uiso(O23)=Uiso(O24)=Uiso(O25)=Uiso(O26)=Uiso(O27)=
 Uiso(O28)=Uiso(O30)=Uiso(O31)=Uiso(O32)=Uiso(O33)=Uiso(O34)=Uiso(O35)=
 Uiso(O36)=Uiso(O37)=Uiso(O38)=Uiso(O39)=Uiso(O40)=Uiso(O41)=Uiso(O42)=FVAR(1)
 Fixed Sof: H27(0.5) H27A(0.5) O7(0.5) O8(0.5) C28(0.5) C29(0.5) H29(0.5)
 C30(0.5) H30(0.5) C31(0.5) H31(0.5) C32(0.5) H32(0.5) C33(0.5) C34(0.5)
 O7C(0.5) O8C(0.5) C28C(0.5) C29C(0.5) H29C(0.5) C30C(0.5) H30C(0.5) C31C(0.5)
 H31C(0.5) C32C(0.5) H32C(0.5) C33C(0.5) C34C(0.5) O5(0.5) O6(0.5) O5C(0.5)
 O6C(0.5) H27B(0.5) H27C(0.5) O7A(0.5) O8A(0.5) C28A(0.5) C29A(0.5) H29A(0.5)
 C30A(0.5) H30A(0.5) C31A(0.5) H31A(0.5) C32A(0.5) H32A(0.5) C33A(0.5)
 C34A(0.5) O7B(0.5) O8B(0.5) C28B(0.5) C29B(0.5) H29B(0.5) C30B(0.5) H30B(0.5)
 C31B(0.5) H31B(0.5) C32B(0.5) H32B(0.5) C33B(0.5) C34B(0.5) O5A(0.5) O6A(0.5)
 O5B(0.5) O6B(0.5)
6.a Ternary CH refined with riding coordinates:
 C27(H27), C27(H27A), C1(H1), C13(H13), C39(H39), C27A(H27B), C27A(H27C),
 C1A(H1A), C13A(H13A), C39A(H39A), C53G(H53G), C54G(H54G), C53E(H53E),
 C54E(H54E), C53D(H53D), C54D(H54D), C53(H53), C54(H54), C53F(H53F), C54F(H54F),
  C53A(H53A), C54A(H54A), C53B(H53B), C54B(H54B), C53C(H53C), C54C(H54C)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C36(H36A,H36B), C37(H37A,H37B), C10A(H10C,
 H10D), C11A(H11C,H11D), C36A(H36C,H36D), C37A(H37C,H37D), N5G(H5GA,H5GB),
 N5E(H5EA,H5EB), N5D(H5DA,H5DB), N5(H5B,H5C), N5F(H5FA,H5FB), N5A(H5AA,H5AB),
 N5B(H5BA,H5BB), N5C(H5CA,H5CB)
6.c Me refined with riding coordinates:
 C55G(H55A,H55B,H55C), C56G(H56A,H56B,H56C), C55E(H55D,H55E,H55F), C56E(H56D,
 H56E,H56F), C55D(H55G,H55H,H55I), C56D(H56G,H56H,H56I), C55(H55J,H55K,H55L),
 C56(H56J,H56K,H56L), C55F(H55M,H55N,H55O), C56F(H56M,H56N,H56O), C55A(H55P,
 H55Q,H55R), C56A(H56P,H56Q,H56R), C55B(H55S,H55T,H55U), C56B(H56S,H56T,H56U),
 C55C(H55V,H55W,H55X), C56C(H56V,H56W,H56X)
6.d Aromatic/amide H refined with riding coordinates:
 C29(H29), C30(H30), C31(H31), C32(H32), C29C(H29C), C30C(H30C), C31C(H31C),
 C32C(H32C), C3(H3), C4(H4), C5(H5), C6(H6), C15(H15), C16(H16), C17(H17),
 C18(H18), C22(H22), C23(H23), C24(H24), C25(H25), C41(H41), C42(H42), C43(H43),
  C44(H44), C29A(H29A), C30A(H30A), C31A(H31A), C32A(H32A), C29B(H29B),
 C30B(H30B), C31B(H31B), C32B(H32B), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A),
 C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A), C22A(H22A), C23A(H23A),
 C24A(H24A), C25A(H25A), C41A(H41A), C42A(H42A), C43A(H43A), C44A(H44A),
 C47G(H47G), C48G(H48G), C49G(H49G), C50G(H50G), C51G(H51G), C47E(H47E),
 C48E(H48E), C49E(H49E), C50E(H50E), C51E(H51E), C47D(H47D), C48D(H48D),
 C49D(H49D), C50D(H50D), C51D(H51D), C47(H47), C48(H48), C49(H49), C50(H50),
 C51(H51), C47F(H47F), C48F(H48F), C49F(H49F), C50F(H50F), C51F(H51F),
 C47A(H47A), C48A(H48A), C49A(H49A), C50A(H50A), C51A(H51A), C47B(H47B),
 C48B(H48B), C49B(H49B), C50B(H50B), C51B(H51B), C47C(H47C), C48C(H48C),
 C49C(H49C), C50C(H50C), C51C(H51C)
6.e Fitted hexagon refined as free rotating group:
 C28(C29,C30,C31,C32,C33), C28C(C29C,C30C,C31C,C32C,C33C), C2(C3,C4,C5,C6,C7),
 C14(C15,C16,C17,C18,C19), C40(C41,C42,C43,C44,C45), C28A(C29A,C30A,C31A,C32A,
 C33A), C28B(C29B,C30B,C31B,C32B,C33B), C2A(C3A,C4A,C5A,C6A,C7A), C14A(C15A,
 C16A,C17A,C18A,C19A), C40A(C41A,C42A,C43A,C44A,C45A), C47G(C48G,C49G,C50G,C51G,
 C52G), C47E(C48E,C49E,C50E,C51E,C52E), C47D(C48D,C49D,C50D,C51D,C52D), C47(C48,
 C49,C50,C51,C52), C47F(C48F,C49F,C50F,C51F,C52F), C47A(C48A,C49A,C50A,C51A,
 C52A), C47B(C48B,C49B,C50B,C51B,C52B), C47C(C48C,C49C,C50C,C51C,C52C)
6.f Idealised tetrahedral OH refined as rotating group:
 O13G(H13G), O13E(H13E), O13D(H13D), O13(H13B), O13F(H13F), O13A(H13C),
 O13B(H13H), O13C(H13I)
;
_shelx_res_checksum              76614
_shelx_hkl_checksum              95190
_olex2_submission_special_instructions 'No special instructions were received'