Diastereoselective Synthesis of Morphan Derivatives by Michael and Hetero-Michael Addition of 1,1-Enediamines to Quinone Monoketals.
Hu, Xing-Mei; Luo, Da-Yun; Zi, Quan-Xing; Lin, Jun; Yan, Sheng-Jiao; ACS omega 3 (2018) 8–21; doi:10.1021/acsomega.7b01493

data_4515905
_publ_section_title
;
 Diastereoselective Synthesis of Morphan Derivatives by Michael and
 Hetero-Michael Addition of 1,1-Enediamines to Quinone Monoketals.
;
_journal_issue                   1
_journal_name_full               'ACS omega'
_journal_page_first              8
_journal_page_last               21
_journal_paper_doi               10.1021/acsomega.7b01493
_journal_volume                  3
_journal_year                    2018
_chemical_formula_moiety         'C19 H25 N3 O5'
_chemical_formula_sum            'C19 H25 N3 O5'
_chemical_formula_weight         375.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-09-28
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 96.021(2)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   21.969(4)
_cell_length_b                   17.259(3)
_cell_length_c                   20.669(3)
_cell_measurement_reflns_used    3667
_cell_measurement_temperature    297
_cell_measurement_theta_max      20.129
_cell_measurement_theta_min      2.409
_cell_volume                     7794(2)
_computing_cell_refinement       'SAINT v8.34A (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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      297.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scan'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0857
_diffrn_reflns_av_unetI/netI     0.0882
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            28452
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.681
_diffrn_reflns_theta_min         2.360
_diffrn_standards_decay_%        1
_diffrn_standards_interval_count 100
_diffrn_standards_number         1
_exptl_absorpt_coefficient_mu    0.093
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5149
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/3 (Bruker,2014/3) was used for absorption correction. wR2(int) was 0.0806 before and 0.0609 after correction. The Ratio of minimum to maximum transmission is 0.6906. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       block
_exptl_crystal_F_000             3200
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.308
_refine_diff_density_min         -0.251
_refine_diff_density_rms         0.038
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.995
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     566
_refine_ls_number_reflns         7389
_refine_ls_number_restraints     231
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.1522
_refine_ls_R_factor_gt           0.0643
_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^)+(0.0727P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1321
_refine_ls_wR_factor_ref         0.1639
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3590
_reflns_number_total             7389
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao7b01493_si_005.cif
_cod_data_source_block           hxm2bf_0m
_cod_database_code               4515905
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C38A-C34A
 1.4 with sigma of 0.02
 C38-C34
 1.4 with sigma of 0.02
 C34-C33 = C32-C31 = C36-C35
 1.4 with sigma of 0.02
 C34-C35 = C36-C31 = C32-C33
 1.4 with sigma of 0.02
 C34A-C33A = C32A-C31A = C36A-C35A
 1.4 with sigma of 0.02
 C34A-C35A = C36A-C31A = C32A-C33A
 1.4 with sigma of 0.02
 H5-H37A
 2.3 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C38) \\sim Ueq, Uanis(C38A) \\sim Ueq, Uanis(C37A) \\sim Ueq, Uanis(C34A)
\\sim Ueq, Uanis(C33A) \\sim Ueq, Uanis(C32A) \\sim Ueq, Uanis(C31A) \\sim Ueq,
Uanis(C36A) \\sim Ueq, Uanis(C35A) \\sim Ueq, Uanis(N6) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 N6, C31, C31A, C32, C32A, C33, C33A, C34, C34A, C35, C35A, C36, C36A, C37,
 C37A, C38, C38A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H6B)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=
 Sof(C34A)=Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(H36A)=Sof(C37A)=Sof(H37C)=
 Sof(H37D)=Sof(C38A)=Sof(H38C)=Sof(H38D)=1-FVAR(1)
 Sof(H6A)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=
 Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=
 Sof(H38A)=Sof(H38B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C3(H3A), C7(H7), C10(H10), C22(H22), C26(H26), C29(H29)
6.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C12(H12A,H12B), C13(H13A,H13B), C27(H27A,H27B), C37(H37A,H37B),
 C37A(H37C,H37D), C38(H38A,H38B), C38A(H38C,H38D)
6.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N3(H3), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), N5(H5),
 N6(H6A), N6(H6B), C31(H31), C31A(H31A), C32(H32), C32A(H32A), C33(H33),
 C33A(H33A), C35(H35), C35A(H35A), C36(H36), C36A(H36A)
6.d Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6C,H6D,H6E), C11(H11A,H11B,H11C), C24(H24A,H24B,H24C),
 C25(H25A,H25B,H25C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              84013
_shelx_hkl_checksum              46198
_olex2_submission_special_instructions 'No special instructions were received'