A Chiral Pentenolide-Based Unified Strategy toward Dihydrocorynantheal, Dihydrocorynantheol, Protoemetine, Protoemetinol, and Yohimbane.
Xie, Changmin; Luo, Jisheng; Zhang, Yan; Zhu, Lili; Hong, Ran; Organic letters 19 (2017) 3592–3595; doi:10.1021/acs.orglett.7b01573

data_1546364
_publ_section_title
;
 A Chiral Pentenolide-Based Unified Strategy toward Dihydrocorynantheal,
 Dihydrocorynantheol, Protoemetine, Protoemetinol, and Yohimbane.
;
_journal_issue                   13
_journal_name_full               'Organic letters'
_journal_page_first              3592
_journal_page_last               3595
_journal_paper_doi               10.1021/acs.orglett.7b01573
_journal_volume                  19
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C20 H26 N2'
_chemical_formula_sum            'C20 H26 N2'
_chemical_formula_weight         294.43
_space_group_crystal_system      trigonal
_space_group_IT_number           145
_space_group_name_Hall           'P 32'
_space_group_name_H-M_alt        'P 32'
_symmetry_space_group_name_Hall  'P 32'
_symmetry_space_group_name_H-M   'P 32'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-02-08
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   20.168(2)
_cell_length_b                   20.168(2)
_cell_length_c                   11.2557(12)
_cell_measurement_reflns_used    5426
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      19.599
_cell_measurement_theta_min      2.332
_cell_volume                     3964.9(7)
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_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      296.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0363
_diffrn_reflns_av_unetI/netI     0.0521
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            33059
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.720
_diffrn_reflns_theta_min         1.809
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.065
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6870
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2008/1 (Bruker,2008) was used for absorption correction. wR2(int) was 0.0482 before and 0.0421 after correction. The Ratio of minimum to maximum transmission is 0.9214. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.110
_exptl_crystal_description       block
_exptl_crystal_F_000             1440
_refine_diff_density_max         0.283
_refine_diff_density_min         -0.134
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 2245 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.1(9)
_refine_ls_extinction_coef       0.0091(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   0.960
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           fullcycle
_refine_ls_number_parameters     599
_refine_ls_number_reflns         12264
_refine_ls_number_restraints     51
_refine_ls_restrained_S_all      0.989
_refine_ls_R_factor_all          0.1360
_refine_ls_R_factor_gt           0.0526
_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^)+(0.0869P)^2^+0.0129P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1260
_refine_ls_wR_factor_ref         0.1656
_reflns_Friedel_coverage         0.996
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                5796
_reflns_number_total             12264
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            mo_dm17059_0m.cif
_cod_data_source_block           mo_dm17059_0m
_cod_depositor_comments
'Adding full bibliography for 1546362--1546364.cif.'
_cod_original_cell_volume        3964.9(9)
_cod_database_code               1546364
_shelx_shelxl_version_number     2016/6
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.567(2) 0.433(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C18-C17
 1.28 with sigma of 0.02
 C60-C59
 1.52 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C53 \\sim C59 \\sim C60: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
C57 \\sim C58 \\sim C56: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C4) \\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C60) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C58) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5.a Ternary CH refined with riding coordinates:
 C9(H9), C13(H13), C14(H14), C29(H29), C33(H33), C34(H34), C49(H49), C53(H53),
 C54(H54)
5.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C15(H15A,H15B), C16(H16A,
 H16B), C19(H19A,H19B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B),
 C35(H35A,H35B), C36(H36A,H36B), C39(H39A,H39B), C50(H50A,H50B), C51(H51A,H51B),
  C52(H52A,H52B), C55(H55A,H55B), C56(H56A,H56B), C59(H59A,H59B)
5.c Me refined with riding coordinates:
 C60(H60A,H60B,H60C)
5.d Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C17(H17), N3(H3A), C22(H22), C23(H23),
  C24(H24), C25(H25), C37(H37), N5(H5A), C42(H42), C43(H43), C44(H44), C45(H45),
  C57(H57)
5.e X=CH2 refined with riding coordinates:
 C18(H18A,H18B), C38(H38A,H38B), C58(H58A,H58B)
5.f Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              90513
_shelx_hkl_checksum              80653
_olex2_submission_special_instructions 'No special instructions were received'