Rh-Catalyzed Stereospecific Synthesis of Allenes from Propargylic Benzoates and Arylboronic Acids.
Ruchti, Jonathan; Carreira, Erick M.; Organic letters 18 (2016) 2174–2176; doi:10.1021/acs.orglett.6b00793

data_1555544
_publ_section_title
;
 Rh-Catalyzed Stereospecific Synthesis of Allenes from Propargylic
 Benzoates and Arylboronic Acids.
;
_journal_issue                   9
_journal_name_full               'Organic letters'
_journal_page_first              2174
_journal_page_last               2176
_journal_paper_doi               10.1021/acs.orglett.6b00793
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H20 Br N O2'
_chemical_formula_sum            'C22 H20 Br N O2'
_chemical_formula_weight         410.30
_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
_audit_creation_date             2015-10-16
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.712(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.6651(6)
_cell_length_b                   5.8524(3)
_cell_length_c                   18.9495(10)
_cell_measurement_reflns_used    6443
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      30.3890
_cell_measurement_theta_min      2.4340
_cell_volume                     958.94(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.908
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \f   -360.01   9.49   0.50   50.00  16.18  17.00  25.50    --   739
  2  \w    -10.89  27.11   0.50   50.00    --   14.50  70.52-100.02   76
  3  \f      7.86  82.36   0.50   50.00  23.69   9.50 -72.01    --   149
  4  \w     61.23  86.73   0.50   50.00    --    4.50 158.12 132.40   51
;
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker/Nonius Kappa Apex2'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0740056000
_diffrn_orient_matrix_UB_12      -0.0404920000
_diffrn_orient_matrix_UB_13      0.0080296000
_diffrn_orient_matrix_UB_21      0.0340270000
_diffrn_orient_matrix_UB_22      -0.1024679000
_diffrn_orient_matrix_UB_23      0.0135740000
_diffrn_orient_matrix_UB_31      0.0096597000
_diffrn_orient_matrix_UB_32      0.0504147000
_diffrn_orient_matrix_UB_33      0.0340450000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.908
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            5272
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.874
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.665
_diffrn_reflns_theta_min         2.355
_diffrn_source                   'fine-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    2.159
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64688
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.421
_exptl_crystal_description       block
_exptl_crystal_F_000             420
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.465
_refine_diff_density_min         -0.656
_refine_diff_density_rms         0.100
_refine_ls_abs_structure_details
;
 Flack x determined using 1717 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.047(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     239
_refine_ls_number_reflns         5272
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0720
_refine_ls_R_factor_gt           0.0589
_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^)+(0.0436P)^2^+3.3631P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1301
_refine_ls_wR_factor_ref         0.1410
_reflns_Friedel_coverage         0.766
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.833
_reflns_number_gt                4746
_reflns_number_total             5272
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9396\% 
 around [1.00 0.00 -0.00] (reciprocal) or [1.00 0.00 0.03] (direct)
;
_cod_data_source_file            ol6b00793_si_004.cif
_cod_data_source_block           ca101015_1_1_twin1_hklf4
_cod_database_code               1555544
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         'C11 H10 N O'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.768(3) 0.232(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Rigid bond restraints
 Br1, C1, C2, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Rigid body (RIGU) restrains
 Br1, C1, C2, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Secondary CH2 refined with riding coordinates:
 C00B(H00A,H00B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C18(H18), C19(H19), C20(H20), C21(H21)
5.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C)
;
_shelx_res_checksum              9927
_shelx_hkl_checksum              40850
_olex2_date_sample_data_collection 2015-10-15
_olex2_date_sample_submission    2015-10-09
_olex2_submission_original_sample_id ca101015_1_1
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.540
_oxdiff_exptl_absorpt_empirical_full_min 0.761
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2