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_1555546
_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 unk
_chemical_formula_moiety         'C28 H25 N O2'
_chemical_formula_sum            'C28 H25 N O2'
_chemical_formula_weight         407.49
_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
_audit_creation_date             2015-10-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   5.99770(10)
_cell_length_b                   8.66900(10)
_cell_length_c                   42.0392(7)
_cell_measurement_reflns_used    9932
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      66.54
_cell_measurement_theta_min      4.21
_cell_volume                     2185.79(6)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Kappa Apex2 Duo'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0430
_diffrn_reflns_av_unetI/netI     0.0225
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            28660
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         2.102
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.607
_exptl_absorpt_correction_T_max  0.7528
_exptl_absorpt_correction_T_min  0.6567
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0590 before and 0.0493 after correction.
The Ratio of minimum to maximum transmission is 0.8723.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.238
_exptl_crystal_description       block
_exptl_crystal_F_000             864
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.105
_refine_diff_density_min         -0.185
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 1477 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.01(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.075
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         3862
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0317
_refine_ls_R_factor_gt           0.0299
_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^)+(0.0369P)^2^+0.4363P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0721
_refine_ls_wR_factor_ref         0.0732
_reflns_Friedel_coverage         0.685
_reflns_Friedel_fraction_full    0.973
_reflns_Friedel_fraction_max     0.995
_reflns_number_gt                3700
_reflns_number_total             3862
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b00793_si_002.cif
_cod_data_source_block           cu_ca091015_1_1_0m
_cod_database_code               1555546
_shelxl_version_number           2014/6
_olex2_refinement_description
;
1. 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
2.a Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12),
 C15(H15), C23(H23), C24(H24), C25(H25), C26(H26)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              81666
_shelx_hkl_checksum              7746
_olex2_date_sample_data_collection 2015-10-14
_olex2_date_sample_submission    2015-10-09
_olex2_submission_original_sample_id ca091015_1_1
_olex2_submission_special_instructions 'No special instructions were received'