A Concise, Enantioselective Approach for the Synthesis of Yohimbine Alkaloids.
Miller, Eric R.; Hovey, M. Todd; Scheidt, Karl A.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b12319

data_4133986
_publ_section_title
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 A Concise, Enantioselective Approach for the Synthesis of Yohimbine
 Alkaloids.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b12319
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'Cl, C21 H27 N2 O3, C H4 O'
_chemical_formula_sum            'C22 H31 Cl N2 O4'
_chemical_formula_weight         422.94
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-02
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.8504(9)
_cell_length_b                   15.0485(13)
_cell_length_c                   15.7936(14)
_cell_measurement_reflns_used    8135
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.730
_cell_measurement_theta_min      2.638
_cell_volume                     2103.5(3)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0837
_diffrn_reflns_av_unetI/netI     0.0869
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            24460
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.015
_diffrn_reflns_theta_min         1.869
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.213
_exptl_absorpt_correction_T_max  0.7460
_exptl_absorpt_correction_T_min  0.6296
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.1631 before and 0.0717 after correction.
The Ratio of minimum to maximum transmission is 0.8440.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.336
_exptl_crystal_description       needle
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.482
_exptl_crystal_size_mid          0.058
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.258
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 1515 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         6153
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0817
_refine_ls_R_factor_gt           0.0513
_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^)+(0.0578P)^2^+0.0634P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1132
_refine_ls_wR_factor_ref         0.1268
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                4566
_reflns_number_total             6153
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b12319_si_003.cif
_cod_data_source_block           erm_cx1552
_cod_database_code               4133986
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.995
_shelx_estimated_absorpt_t_min   0.904
_olex2_refinement_description
;
1. 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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 N1(H1), C11(H11), C13(H13), C14(H14), C15(H15), C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C12(H12A,H12B), C16(H16A,H16B), C17(H17A,H17B),
 C19(H19A,H19B)
2.c Aromatic/amide H refined with riding coordinates:
 N2(H2), C5(H5), C6(H6), C7(H7), C8(H8)
2.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4)
;
_shelx_res_checksum              11743
_shelx_hkl_checksum              58854
_olex2_submission_special_instructions 'No special instructions were received'