(R)-DM-SEGPHOS-Ag(I)-Catalyzed Enantioselective Synthesis of Pyrrolidines and Pyrrolizidines via (1,3)- and Double (1,3)-Dipolar Cycloaddition Reactions.
Ray, Sumit K.; Biswas, Rayhan G.; Suneja, Arun; Sadhu, Milon M.; Singh, Vinod K.; The Journal of organic chemistry 83 (2018) 2293–2308; doi:10.1021/acs.joc.7b03185

data_4033482
_publ_section_title
;
 (R)-DM-SEGPHOS-Ag(I)-Catalyzed Enantioselective Synthesis of Pyrrolidines
 and Pyrrolizidines via (1,3)- and Double (1,3)-Dipolar Cycloaddition
 Reactions.
;
_journal_issue                   4
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2293
_journal_page_last               2308
_journal_paper_doi               10.1021/acs.joc.7b03185
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C42 H35 Br N4 O5, C2 H6 O'
_chemical_formula_sum            'C44 H41 Br N4 O6'
_chemical_formula_weight         801.72
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-09-08
_audit_creation_method
;
Olex2 1.2-dev
(compiled 2017.07.26 svn.r3458 for OlexSys, GUI svn.r5356)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9679(2)
_cell_length_b                   17.7320(3)
_cell_length_c                   20.2762(4)
_cell_measurement_reflns_used    10575
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.2
_cell_volume                     3943.37(13)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      296
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEXII CCD area-detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0440
_diffrn_reflns_av_unetI/netI     0.0658
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            45656
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.082
_diffrn_reflns_theta_min         2.009
_exptl_absorpt_coefficient_mu    1.096
_exptl_absorpt_correction_type   none
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.350
_exptl_crystal_description       needle
_exptl_crystal_F_000             1664
_exptl_crystal_size_max          0.50
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.507
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.052
_refine_ls_abs_structure_details
;
 Flack x determined using 3247 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.005(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.974
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     540
_refine_ls_number_reflns         11492
_refine_ls_number_restraints     68
_refine_ls_restrained_S_all      0.976
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0381
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0330P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0738
_refine_ls_wR_factor_ref         0.0789
_reflns_Friedel_coverage         0.812
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                8927
_reflns_number_total             11492
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo7b03185_si_004.cif
_cod_data_source_block           rgb_590
_cod_depositor_comments
'Adding full bibliography for 4033482--4033485.cif.'
_cod_database_code               4033482
_shelx_shelxl_version_number     2017/1
_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. Restrained distances
 C3-C4
 1.51 with sigma of 0.02
 C3-O2
 1.425 with sigma of 0.02
 C4-O2
 2.366 with sigma of 0.03
 C1-C2
 1.51 with sigma of 0.02
 C1-O1
 1.425 with sigma of 0.02
 C2-O1
 2.366 with sigma of 0.03
 C5-C6
 1.51 with sigma of 0.02
 C5-O3
 1.425 with sigma of 0.02
 C6-O3
 2.366 with sigma of 0.03
 O2-C4 \\sim O1-C2 \\sim O3-C6
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
O2 \\sim C3 \\sim C4: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
O1 \\sim C1 \\sim C2: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
O3 \\sim C5 \\sim C6: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uiso(O3) = Uiso(C5) = Uiso(C6)
4. Rigid body (RIGU) restrains
 O2, C3, C4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O1, C1, C2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C4, O2, C3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O3, C5, C6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Fixed Sof: O2(0.6) H2(0.6) C3(0.6) H3A(0.6) H3B(0.6) C4(0.6) H4A(0.6)
 H4B(0.6) H4C(0.6) O1(0.3) H1(0.3) C1(0.3) H1A(0.3) H1B(0.3) C2(0.3) H2A(0.3)
 H2B(0.3) H2C(0.3) O3(0.1) H3(0.1) C5(0.1) H5A(0.1) H5B(0.1) C6(0.1) H6A(0.1)
 H6B(0.1) H6C(0.1)
6.a Ternary CH refined with riding coordinates:
 C00G(H00G), C00I(H00I), C00K(H00K), C00P(H00P), C00S(H00S), C00W(H00W)
6.b Secondary CH2 refined with riding coordinates:
 C014(H01A,H01B), C3(H3A,H3B), C1(H1A,H1B), C5(H5A,H5B)
6.c Aromatic/amide H refined with riding coordinates:
 C00F(H00F), C00J(H00J), C00N(H00N), C00Q(H00Q), C00R(H00R), C00X(H00X),
 C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011), C012(H012), C013(H013),
 C015(H015), C016(H016), C017(H017), C018(H018), C019(H019), C01A(H01C),
 C01B(H01D), C01C(H01E), C01D(H01F), C01E(H01G), C01F(H01H), C01G(H01I)
6.d Idealised Me refined as rotating group:
 C01H(H01J,H01K,H01L), C4(H4A,H4B,H4C), C2(H2A,H2B,H2C), C6(H6A,H6B,H6C)
6.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O1(H1), O3(H3)
;
_shelx_res_checksum              3765
_shelx_hkl_checksum              76284
_olex2_submission_special_instructions 'No special instructions were received'