Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination.
Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong; Journal of the American Chemical Society 139 (2017) 5558–5567; doi:10.1021/jacs.7b01718

data_4125904
_publ_section_title
;
 Total Synthesis and Stereochemical Assignment of Delavatine A:
 Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted
 Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed
 C-H Olefination.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5558
_journal_page_last               5567
_journal_paper_doi               10.1021/jacs.7b01718
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_sum            'C13 H16 F3 N O3 S'
_chemical_formula_weight         323.33
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.2899(5)
_cell_length_b                   9.3662(9)
_cell_length_c                   29.113(3)
_cell_measurement_reflns_used    3451
_cell_measurement_temperature    140(2)
_cell_measurement_theta_max      25.55
_cell_measurement_theta_min      2.28
_cell_volume                     1442.4(2)
_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-2014 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      140(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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  0.0383
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       41
_diffrn_reflns_limit_l_min       -41
_diffrn_reflns_number            14544
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.495
_diffrn_reflns_theta_min         2.284
_exptl_absorpt_coefficient_mu    0.267
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6796
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   sadabs
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_description       block
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.150
_refine_diff_density_max         0.352
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
; 
 Flack x determined using 1318 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   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         4399
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0543
_refine_ls_R_factor_gt           0.0423
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0468P)^2^+0.1112P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0934
_refine_ls_wR_factor_ref         0.0991
_reflns_Friedel_coverage         0.712
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                3679
_reflns_number_total             4399
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b01718_si_002.cif
_cod_data_source_block           mo_dm14335_0m
_cod_depositor_comments
'Adding full bibliography for 4125903--4125907.cif.'
_cod_original_cell_volume        1442.5(2)
_cod_database_code               4125904
_shelx_estimated_absorpt_t_min   0.936
_shelx_estimated_absorpt_t_max   0.961
_shelxl_version_number           2014-3
_shelx_res_checksum              20028
_shelx_hkl_checksum              30800