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_4133987
_publ_section_title
;
 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         'C2 F3 O2, C22 H29 N2 O4'
_chemical_formula_sum            'C24 H29 F3 N2 O6'
_chemical_formula_weight         498.49
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-11-13
_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                 91.701(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4230(12)
_cell_length_b                   8.3502(8)
_cell_length_c                   23.217(2)
_cell_measurement_reflns_used    9880
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      65.324
_cell_measurement_theta_min      6.531
_cell_volume                     2407.3(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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      99.99
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.988
_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  0.0209
_diffrn_reflns_av_unetI/netI     0.0256
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            17945
_diffrn_reflns_point_group_measured_fraction_full 0.938
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        65.320
_diffrn_reflns_theta_max         65.319
_diffrn_reflns_theta_min         5.631
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.970
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6689
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0411 before and 0.0317 after correction.
The Ratio of minimum to maximum transmission is 0.8888.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.375
_exptl_crystal_description       needle
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.374
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.063
_refine_diff_density_max         0.448
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.040
_refine_ls_abs_structure_details
;
 Flack x determined using 3231 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     635
_refine_ls_number_reflns         7734
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0316
_refine_ls_R_factor_gt           0.0310
_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^)+(0.0420P)^2^+0.8652P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0794
_refine_ls_wR_factor_ref         0.0799
_reflns_Friedel_coverage         0.763
_reflns_Friedel_fraction_full    0.879
_reflns_Friedel_fraction_max     0.879
_reflns_number_gt                7593
_reflns_number_total             7734
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b12319_si_002.cif
_cod_data_source_block           erm_cx1440
_cod_original_cell_volume        2407.4(4)
_cod_database_code               4133987
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.941
_shelx_estimated_absorpt_t_min   0.713
_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
2.a Ternary CH refined with riding coordinates:
 N00K(H00K), N2(H2), C01E(H01E), C01I(H01I), C11(H11), C13(H13), C017(H017),
 C18(H18)
2.b Secondary CH2 refined with riding coordinates:
 C00X(H00A,H00B), C1(H1A,H1B), C01G(H01A,H01B), C01K(H01D,H01F), C01M(H01G,
 H01H), C01R(H01J,H01K), C01U(H01L,H01M), C2(H2A,H2B), C12(H12A,H12B),
 C013(H01W,H01X), C15(H15A,H15B), C17(H17A,H17B), C19(H19A,H19B), C21(H21A,H21B)
2.c Aromatic/amide H refined with riding coordinates:
 N00G(H00G), N1(H1), C01C(H01C), C01N(H01N), C01Q(H01Q), C01T(H01T), C5(H5),
 C6(H6), C7(H7), C8(H8)
2.d Idealised Me refined as rotating group:
 C01V(H01O,H01P,H01R), C01W(H01S,H01U,H01V), C16(H16A,H16B,H16C), C22(H22A,
 H22B,H22C)
;
_shelx_res_checksum              38951
_shelx_hkl_checksum              77470
_olex2_submission_special_instructions 'No special instructions were received'