Enantioselective intramolecular C-h insertion reactions of donor-donor metal carbenoids.
Soldi, Cristian; Lamb, Kellan N.; Squitieri, Richard A.; González-López, Marcos; Di Maso, Michael J.; Shaw, Jared T.; Journal of the American Chemical Society 136 (2014) 15142–15145; doi:10.1021/ja508586t

data_4122833
_publ_section_title
;
 Enantioselective intramolecular C-h insertion reactions of donor-donor
 metal carbenoids.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15142
_journal_page_last               15145
_journal_paper_doi               10.1021/ja508586t
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H18 O2'
_chemical_formula_sum            'C21 H18 O2'
_chemical_formula_weight         302.35
_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
_atom_sites_solution_primary     direct
_audit_creation_date             2014-08-07
_audit_creation_method
;
Olex2 1.2
(compiled 2014.07.22 svn.r2960 for OlexSys, GUI svn.r4862)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.7265(2)
_cell_length_b                   12.1931(3)
_cell_length_c                   22.4695(5)
_cell_measurement_reflns_used    4373
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      68.11
_cell_measurement_theta_min      7.26
_cell_volume                     1568.91(8)
_computing_cell_refinement       'SAINT (Bruker, 2011)'
_computing_data_collection       'Apex2 (Bruker, 2011)'
_computing_data_reduction        'SAINT (Bruker, 2011)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      90.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'Bruker DUO'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0445
_diffrn_reflns_av_unetI/netI     0.0337
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            11863
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         69.003
_diffrn_reflns_theta_min         7.264
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.639
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.6685
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0879 before and 0.0487 after correction.
The Ratio of minimum to maximum transmission is 0.8877.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear ? colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       block
_exptl_crystal_F_000             640
_exptl_crystal_size_max          0.257
_exptl_crystal_size_mid          0.253
_exptl_crystal_size_min          0.192
_refine_diff_density_max         0.181
_refine_diff_density_min         -0.136
_refine_diff_density_rms         0.031
_refine_ls_abs_structure_details
;
 Flack x determined using 1037 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.09(14)
_refine_ls_extinction_coef       0.0022(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     210
_refine_ls_number_reflns         2863
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0362
_refine_ls_R_factor_gt           0.0314
_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^)+(0.0366P)^2^+0.1293P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0729
_refine_ls_wR_factor_ref         0.0750
_reflns_Friedel_coverage         0.690
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.977
_reflns_number_gt                2616
_reflns_number_total             2863
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja508586t_si_001.cif
_cod_data_source_block           cu_mdm1_0m
_cod_depositor_comments          'Adding full bibliography for 4122833.cif.'
_cod_database_code               4122833
_shelxl_version_number           2012-9
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C1(H1)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C11(H11), C10(H10), C16(H16), C17(H17), C20(H20), C19(H19),
 C13(H13), C14(H14), C4(H4), C5(H5), C6(H6), C7(H7)
2.c Idealised Me refined as rotating group:
 C21(H21a,H21b,H21c)
;
_olex2_submission_special_instructions 'No special instructions were received'