Intramolecular β-Alkenylation of Cyclohexanones via Pd-Catalyzed Desaturation-Mediated C(sp3)-H/Alkyne Coupling.
Wang, Chengpeng; Naren, Nevin A.; Zheng, Pengfei; Dong, Guangbin; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c02654

data_4134862
_publ_section_title
;
 Intramolecular \b-Alkenylation of Cyclohexanones via Pd-Catalyzed
 Desaturation-Mediated C(sp3)-H/Alkyne Coupling.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c02654
_journal_year                    2020
_chemical_formula_moiety         'C15 H18 O4'
_chemical_formula_sum            'C15 H18 O4'
_chemical_formula_weight         262.29
_chemical_name_systematic        wcp-8-165
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-01-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.8814(14)
_cell_length_b                   5.9438(4)
_cell_length_c                   21.4591(15)
_cell_measurement_reflns_used    9398
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      21.26
_cell_measurement_theta_min      2.79
_cell_volume                     2535.8(3)
_computing_cell_refinement       'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX3 v.2015.9-0 (Bruker AXS Inc., 2015)'
_computing_data_reduction        'SAINT V.8.35A (Bruker AXS Inc., 2013)'
_computing_molecular_graphics
;
OLEX2: a complete structure solution, refinement and analysis program 
Dolomanov et al., 2009

Mercury: visualization and analysis of crystal structures
Macrae, et al., 2006

O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann.
J. Appl. Cryst. (2009). 42, 339-341;

C. F. Macrae, P. R. Edgington, P. McCabe, E. Pidcock, G. P. Shields, R. Taylor,
M. Towler and J. van de Streek, J. Appl. Cryst. (2006). 39, 453-457.
;
_computing_publication_material
;
 APEX3 v.2015.5-2 (Bruker AXS Inc., 2015)
 OLEX2 (Dolomanov et al., 2009)
;
_computing_structure_refinement  'XL-2018/3 (Sheldrick, 2015b)'
_computing_structure_solution    'XT 2014/5 (Sheldrick, 2015a)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON 100'
_diffrn_detector_area_resol_mean 10.4167
_diffrn_detector_type            CMOS
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       'omega and phi scans'
_diffrn_radiation_monochromator  mirrors
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1280
_diffrn_reflns_av_unetI/netI     0.0712
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            65551
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.001
_diffrn_reflns_theta_min         2.049
_diffrn_source                   'micro-focus X-ray tube'
_diffrn_source_type              'INCOATEC ImuS'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.099
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6909
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1014 before and 0.0572 after correction.
The Ratio of minimum to maximum transmission is 0.9266.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.374
_exptl_crystal_description       plate
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.301
_exptl_crystal_size_mid          0.109
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.360
_refine_diff_density_min         -0.330
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Flack x determined using 1594 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.3(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.164
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     347
_refine_ls_number_reflns         6099
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.164
_refine_ls_R_factor_all          0.1168
_refine_ls_R_factor_gt           0.0779
_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^)+5.5780P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1224
_refine_ls_wR_factor_ref         0.1333
_reflns_Friedel_coverage         0.944
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                4471
_reflns_number_total             6099
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c02654_si_003.cif
_cod_data_source_block           mono
_cod_database_code               4134862
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.971
_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 O(H) groups
2.a Ternary CH refined with riding coordinates:
 C00D(H00D), C00E(H00E), C5(H5), C00P(H00P), C9(H9), C4(H4A)
2.b Secondary CH2 refined with riding coordinates:
 C00F(H00C,H00F), C2(H2A,H2B), C00N(H00G,H00I), C6(H6A,H6B), C7(H7A,H7B),
 C3(H3A,H3B), C00T(H00J,H00K), C00X(H00L,H00N)
2.c Aromatic/amide H refined with riding coordinates:
 C009(H009), C00A(H00A), C00B(H00B), C00H(H00H), C00M(H00M), C14(H14),
 C13(H13), C12(H12), C11(H11), C15(H15)
2.d Idealised tetrahedral OH refined as rotating group:
 O4(H4), O3(H3), O006(H006), O008(H008)
;
_shelx_res_checksum              9559
_shelx_hkl_checksum              52929
_olex2_submission_original_sample_id wcp-8-165
_olex2_submission_special_instructions 'No special instructions were received'