Bifunctional Ligand-Assisted Catalytic Ketone α-Alkenylation with Internal Alkynes: Controlled Synthesis of Enones and Mechanistic Studies.
Mo, Fanyang; Lim, Hee Nam; Dong, Guangbin; Journal of the American Chemical Society 137 (2015) 15518–15527; doi:10.1021/jacs.5b10466

data_4129788
_publ_section_title
;
 Bifunctional Ligand-Assisted Catalytic Ketone \a-Alkenylation with
 Internal Alkynes: Controlled Synthesis of Enones and Mechanistic Studies.
;
_journal_issue                   49
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15518
_journal_page_last               15527
_journal_paper_doi               10.1021/jacs.5b10466
_journal_volume                  137
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C11 H11 N2 O, 2 C18 H15 P, Rh, H, Cl'
_chemical_formula_sum            'C47 H42 Cl N2 O P2 Rh'
_chemical_formula_weight         851.12
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.962(3)
_cell_length_b                   9.9135(6)
_cell_length_c                   12.5334(11)
_cell_measurement_reflns_used    10727
_cell_measurement_temperature    163(2)
_cell_measurement_theta_max      32.0
_cell_measurement_theta_min      2.0
_cell_volume                     3971.3(6)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2008)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2008)'
_computing_molecular_graphics    'XP SHELXTL/PC, Siemens Analytical'
_computing_structure_refinement  'XL SHELXTL/PC, Siemens Analytical'
_computing_structure_solution
;

SIR97 - Altomare A., Burla M.C., Camalli M., Cascarano G.L., Giacovazzo C., 
Guagliardi A., Moliterni A.G.G., Polidori G.,Spagna R.
;
_diffrn_ambient_temperature      163(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Rigaku SCX-Mini with Mercury 2+ CCD'
_diffrn_measurement_method       \w-scans
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71075
_diffrn_reflns_av_R_equivalents  0.0642
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            71933
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.497
_diffrn_reflns_theta_min         2.065
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.617
_exptl_absorpt_correction_T_max  1.00
_exptl_absorpt_correction_T_min  0.825
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.424
_exptl_crystal_description       prisms
_exptl_crystal_F_000             1752
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.534
_refine_diff_density_min         -0.670
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Flack x determined using 3617 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.025(13)
_refine_ls_extinction_coef       0.00059(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     514
_refine_ls_number_reflns         9112
_refine_ls_number_restraints     26
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0323P)^2^+3.0125P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0897
_refine_ls_wR_factor_ref         0.0919
_reflns_Friedel_coverage         0.911
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                8623
_reflns_number_total             9112
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b10466_si_020.cif
_cod_data_source_block           shelx
_cod_original_cell_volume        3971.3(5)
_cod_database_code               4129788
_shelx_shelxl_version_number     2014/7
_shelx_res_checksum              12303
_shelx_hkl_checksum              61028