Reductive Elimination at Carbon under Steric Control.
Tolentino, Daniel R.; Neale, Samuel E.; Isaac, Connie J.; Macgregor, Stuart A.; Whittlesey, Michael K.; Jazzar, Rodolphe; Bertrand, Guy; Journal of the American Chemical Society 141 (2019) 9823–9826; doi:10.1021/jacs.9b04957

data_4128287
_publ_section_title
;
 Reductive Elimination at Carbon under Steric Control.
;
_journal_issue                   25
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9823
_journal_page_last               9826
_journal_paper_doi               10.1021/jacs.9b04957
_journal_volume                  141
_journal_year                    2019
_chemical_absolute_configuration syn
_chemical_formula_moiety         '1(C34 H48 N2 O)'
_chemical_formula_sum            'C34 H48 N2 O'
_chemical_formula_weight         500.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-05-07
_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                 91.822(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6372(7)
_cell_length_b                   16.6939(12)
_cell_length_c                   16.7043(13)
_cell_measurement_reflns_used    5108
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      20.63
_cell_measurement_theta_min      2.24
_cell_volume                     2964.8(4)
_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)'
_diffrn_ambient_temperature      100.0
_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 0.998
_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           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0556
_diffrn_reflns_av_unetI/netI     0.0803
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            30979
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.426
_diffrn_reflns_theta_min         1.220
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.066
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6915
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0704 before and 0.0512 after correction. The Ratio of minimum to maximum transmission is 0.9279. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.122
_exptl_crystal_description       block
_exptl_crystal_F_000             1096
_exptl_crystal_size_max          0.74
_exptl_crystal_size_mid          0.56
_exptl_crystal_size_min          0.33
_refine_diff_density_max         0.313
_refine_diff_density_min         -0.236
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details
;
 Flack x determined using 2902 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.4(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     744
_refine_ls_number_reflns         10916
_refine_ls_number_restraints     213
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0925
_refine_ls_R_factor_gt           0.0605
_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^)+(0.0544P)^2^+1.0705P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1236
_refine_ls_wR_factor_ref         0.1369
_reflns_Friedel_coverage         0.925
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                8146
_reflns_number_total             10916
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            6_MenthCAACOCNPh.cif
_cod_data_source_block           6_menthcaacocnph
_cod_database_code               4128287
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.952
_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. Restrained distances
 C32B-C34B
 1.532 with sigma of 0.02
 C9A-C31B \\sim C9A-C31A
 with sigma of 0.02
 C9A-C26B \\sim C9A-C26A
 with sigma of 0.02
 C31B-C30B \\sim C31A-C30A
 with sigma of 0.02
 C31B-C32B \\sim C31A-C32A
 with sigma of 0.02
 C26B-C27B \\sim C26A-C27A
 with sigma of 0.02
 C34B-C32B \\sim C33A-C32A
 with sigma of 0.02
 C30B-C29B \\sim C30A-C29A
 with sigma of 0.02
 C27B-C29B \\sim C27A-C29A
 with sigma of 0.02
 C27B-C28B \\sim C27A-C28A
 with sigma of 0.02
 C32B-C33B \\sim C32A-C34A
 with sigma of 0.02
 C9A-C30B \\sim C9A-C30A
 with sigma of 0.04
 C9A-C27B \\sim C9A-C27A
 with sigma of 0.04
 C9A-C32B \\sim C9A-C32A
 with sigma of 0.04
 C31B-C34B \\sim C31A-C33A
 with sigma of 0.04
 C31B-C29B \\sim C31A-C29A
 with sigma of 0.04
 C31B-C33B \\sim C31A-C34A
 with sigma of 0.04
 C26B-C29B \\sim C26A-C29A
 with sigma of 0.04
 C26B-C28B \\sim C26A-C28A
 with sigma of 0.04
 C34B-C33B \\sim C33A-C34A
 with sigma of 0.04
 C30B-C27B \\sim C30A-C27A
 with sigma of 0.04
 C30B-C32B \\sim C30A-C32A
 with sigma of 0.04
 C29B-C28B \\sim C29A-C28A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C4B) = Uanis(C4A)
Uanis(C7A) = Uanis(C7B)
Uanis(C3A) = Uanis(C3B)
Uanis(C8A) = Uanis(C8B)
Uanis(C29B) = Uanis(C29A)
Uanis(C27B) = Uanis(C27A)
Uanis(C31B) = Uanis(C31A)
Uanis(C32B) = Uanis(C32A)
Uanis(C34B) = Uanis(C33A)
Uanis(C26B) = Uanis(C26A)
Uanis(C10A) = Uanis(C10B)
4. Rigid body (RIGU) restrains
 C9A, C26B, C27B, C28B, C29B, C30B, C31B, C32B, C34B, C33B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C9A, C26A, C27A, C28A, C29A, C30A, C31A, C32A, C33A, C34A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C3A, C4A, C5A, C6A, C7A, C8A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C11A, C10B, C9A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
 C9A, C10A, C11A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C3A)=Sof(C8A)=Sof(H8A)=Sof(C7A)=Sof(H7A)=Sof(C6A)=Sof(H6A)=Sof(C5A)=
 Sof(H5A)=Sof(C4A)=Sof(H4A)=1-FVAR(1)
 Sof(C3B)=Sof(C8B)=Sof(H8B)=Sof(C7B)=Sof(H7B)=Sof(C6B)=Sof(H6B)=Sof(C5B)=
 Sof(H5B)=Sof(C4B)=Sof(H4B)=FVAR(1)
 Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C26A)=Sof(H26C)=Sof(H26D)=
 Sof(C31A)=Sof(H31A)=Sof(C30A)=Sof(H30C)=Sof(H30D)=Sof(C29A)=Sof(H29C)=
 Sof(H29D)=Sof(C27A)=Sof(H27A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33D)=
 Sof(H33E)=Sof(H33F)=Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C10A)=
 Sof(H10C)=Sof(H10D)=1-FVAR(2)
 Sof(C31B)=Sof(H31B)=Sof(C10B)=Sof(H10A)=Sof(H10B)=Sof(C26B)=Sof(H26A)=
 Sof(H26B)=Sof(C34B)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C30B)=Sof(H30A)=
 Sof(H30B)=Sof(C27B)=Sof(H27B)=Sof(C29B)=Sof(H29A)=Sof(H29B)=Sof(C32B)=
 Sof(H32B)=Sof(C28B)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C33B)=Sof(H33A)=
 Sof(H33B)=Sof(H33C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C23(H23), C23A(H23A), C20A(H20A), C20(H20), C32(H32), C31(H31), C31B(H31B),
 C27(H27), C27B(H27B), C32B(H32B), C31A(H31A), C27A(H27A), C32A(H32A)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10E,H10F), C29(H29E,H29F), C26(H26E,H26F), C30(H30E,H30F), C10B(H10A,
 H10B), C26B(H26A,H26B), C30B(H30A,H30B), C29B(H29A,H29B), C26A(H26C,H26D),
 C30A(H30C,H30D), C29A(H29C,H29D), C10A(H10C,H10D)
6.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C18(H18), C16(H16), C18A(H18A), C17A(H17A), C16A(H16A), C8(H8),
 C5(H5), C6(H6), C7(H7), C17(H17), C8B(H8B), C7B(H7B), C6B(H6B), C5B(H5B),
 C4B(H4B), C8A(H8A), C7A(H7A), C6A(H6A), C5A(H5A), C4A(H4A)
6.d Fitted hexagon refined as free rotating group:
 C3B(C8B,C7B,C6B,C5B,C4B), C3A(C8A,C7A,C6A,C5A,C4A)
6.e Idealised Me refined as rotating group:
 C25(H25D,H25E,H25F), C12A(H12A,H12B,H12C), C13A(H13A,H13B,H13C), C24A(H24A,
 H24B,H24C), C21A(H21A,H21B,H21C), C34(H34G,H34H,H34I), C12(H12D,H12E,H12F),
 C22A(H22A,H22B,H22C), C25A(H25A,H25B,H25C), C13(H13D,H13E,H13F), C24(H24D,H24E,
 H24F), C21(H21D,H21E,H21F), C33(H33G,H33H,H33I), C22(H22D,H22E,H22F),
 C34B(H34A,H34B,H34C), C28(H28G,H28H,H28I), C28B(H28A,H28B,H28C), C33B(H33A,
 H33B,H33C), C28A(H28D,H28E,H28F), C33A(H33D,H33E,H33F), C34A(H34D,H34E,H34F)
;
_shelx_res_checksum              24326
_shelx_hkl_checksum              66186
_olex2_submission_special_instructions 'No special instructions were received'