Efficient Syntheses of (-)-Crinine and (-)-Aspidospermidine, and Formal Synthesis of (-)-Minfiensine by Enantioselective Intramolecular Dearomative Cyclization
Tang, Wenjun; Du, Kang; Yang, He; Guo, Pan; Feng, Liang; Xu, Guangqing; Zhou, Qing-Hai; Chung, Lung Wa; Chem. Sci.  (2017) –; doi:10.1039/C7SC01859B

data_1546441
_publ_section_title
;
 Efficient Syntheses of (-)-Crinine and (-)-Aspidospermidine, and Formal
 Synthesis of (-)-Minfiensine by Enantioselective Intramolecular
 Dearomative Cyclization
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC01859B
_journal_year                    2017
_chemical_formula_sum            'C20 H32 N3 O6 P'
_chemical_formula_weight         441.45
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method           SHELXL-2013
_audit_update_record
;
2015-12-29 deposited with the CCDC.
2017-07-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.8092(4)
_cell_length_b                   22.5105(7)
_cell_length_c                   8.1573(3)
_cell_measurement_reflns_used    6103
_cell_measurement_temperature    223(2)
_cell_measurement_theta_max      69.65
_cell_measurement_theta_min      3.93
_cell_volume                     2168.46(13)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      223(2)
_diffrn_measured_fraction_theta_full 0.938
_diffrn_measured_fraction_theta_max 0.936
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0335
_diffrn_reflns_av_unetI/netI     0.0395
_diffrn_reflns_Laue_measured_fraction_full 0.938
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            10772
_diffrn_reflns_point_group_measured_fraction_full 0.896
_diffrn_reflns_point_group_measured_fraction_max 0.893
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         67.965
_diffrn_reflns_theta_min         3.927
_exptl_absorpt_coefficient_mu    1.483
_exptl_absorpt_correction_T_max  0.753
_exptl_absorpt_correction_T_min  0.474
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.352
_exptl_crystal_description       block
_exptl_crystal_F_000             944
_exptl_crystal_size_max          0.390
_exptl_crystal_size_mid          0.290
_exptl_crystal_size_min          0.270
_refine_diff_density_max         0.361
_refine_diff_density_min         -0.319
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
; 
 Flack x determined using 1295 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.026(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     291
_refine_ls_number_reflns         3536
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0352
_refine_ls_R_factor_gt           0.0339
_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^)+(0.0567P)^2^+0.0896P] 
 where P=(Fo^2^+2Fc^2^)/3 
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0881
_refine_ls_wR_factor_ref         0.0891
_reflns_Friedel_coverage         0.659
_reflns_Friedel_fraction_full    0.839
_reflns_Friedel_fraction_max     0.835
_reflns_number_gt                3394
_reflns_number_total             3536
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc01859b2.cif
_cod_data_source_block           cu_50512aa
_cod_database_code               1546441
_shelx_estimated_absorpt_t_min   0.595
_shelx_estimated_absorpt_t_max   0.690
_shelxl_version_number           2013-2
_shelx_res_checksum              79723