Pd(ii)-catalyzed β- and γ-C-(sp<sup>3</sup>)-H dienylation with allenyl acetates.
Shukla, Rahul K.; Nair, Akshay M.; Volla, Chandra M. R.; Chemical science 14 (2023) 955–962; doi:10.1039/d2sc05188e

data_1568220
_publ_section_title
;
 Pd(ii)-catalyzed &#x3b2;- and &#x3b3;-C-(sp<sup>3</sup>)-H dienylation
 with allenyl acetates.
;
_journal_issue                   4
_journal_name_full               'Chemical science'
_journal_page_first              955
_journal_page_last               962
_journal_paper_doi               10.1039/d2sc05188e
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         '0.16(C20 H19 N3 O Pd)'
_chemical_formula_sum            'C H N O Pd'
_chemical_formula_weight         149.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-02-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-07-12 deposited with the CCDC.	2022-12-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.717(2)
_cell_angle_gamma                90
_cell_formula_units_Z            49
_cell_length_a                   18.5183(3)
_cell_length_b                   9.40820(10)
_cell_length_c                   20.3888(2)
_cell_measurement_reflns_used    22705
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.7060
_cell_measurement_theta_min      4.4410
_cell_volume                     3465.08(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -191.00 -11.00   0.50    4.00    -- -101.00   0.00 -36.00  360
  2  \w   -122.00  58.00   0.50    4.00    --  -32.00   0.00  36.00  360
  3  \w   -107.00 -11.00   0.50    4.00    -- -101.00  72.00-108.00  192
  4  \w   -104.50 -11.00   0.50    4.00    -- -101.00  72.00 108.00  187
  5  \w   -107.00 -11.00   0.50    4.00    -- -101.00  72.00 -36.00  192
  6  \w    -96.50 -15.50   0.50    4.00    -- -101.00  72.00  36.00  162
  7  \w   -105.50 -22.00   0.50    4.00    -- -101.00  72.00-180.00  167
  8  \w    -65.00  39.00   0.50    4.00    --  -32.00  72.00  36.00  208
  9  \w    -53.00 -21.00   0.50    4.00    --  -32.00  72.00-180.00   64
 10  \w   -189.50 -78.00   0.50    4.00    -- -101.00 -72.00 108.00  223
 11  \w   -188.00 -71.00   0.50    4.00    -- -101.00 -72.00-180.00  234
 12  \w    -40.00 -10.00   0.50    4.00    --  -32.00 -72.00-108.00   60
 13  \w   -189.00 -77.00   0.50    4.00    -- -101.00 -72.00-108.00  224
 14  \w   -191.00-121.00   0.50    4.00    -- -101.00 -72.00 -36.00  140
 15  \w   -191.00-161.00   0.50    4.00    -- -101.00 -72.00  36.00   60
 16  \w   -191.00 -42.00   0.50    4.00    -- -101.00   0.00 108.00  298
 17  \w    -56.00  58.00   0.50    4.00    --  -32.00  72.00-108.00  228
 18  \w   -189.50 -46.00   0.50    4.00    -- -101.00   0.00-108.00  287
 19  \w    -56.00  58.00   0.50    4.00    --  -32.00  72.00 108.00  228
 20  \w    -76.50 -14.50   0.50    4.00    --  -32.00 -72.00 -36.00  124
 21  \w    -79.00   1.00   0.50    4.00    --  -32.00 -72.00  36.00  160
 22  \w    -73.50   2.00   0.50    4.00    --  -32.00 -72.00-180.00  151
 23  \w    -44.00 -14.00   0.50    4.00    --  -32.00 -72.00 108.00   60
 24  \w    -49.00  -2.00   0.50    4.00    --  -32.00  72.00 -36.00   94
 25  \w   -147.00-116.00   0.50    4.00    -- -101.00   0.00  36.00   62
 26  \w   -191.00 -11.00   0.50    4.00    -- -101.00   0.00-180.00  360
 27  \w    -91.00  58.00   0.50    4.00    --  -32.00   0.00 -36.00  298
 28  \w    -88.00 -52.00   0.50    4.00    --  -32.00   0.00 108.00   72
 29  \w    -91.00  58.00   0.50    4.00    --  -32.00   0.00-180.00  298
 30  \w    -16.00  57.00   0.50    4.00    --  -32.00   0.00-108.00  146
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0380704000
_diffrn_orient_matrix_UB_12      0.1270272000
_diffrn_orient_matrix_UB_13      0.0413317000
_diffrn_orient_matrix_UB_21      0.0081627000
_diffrn_orient_matrix_UB_22      0.0743719000
_diffrn_orient_matrix_UB_23      -0.0652946000
_diffrn_orient_matrix_UB_31      -0.0758518000
_diffrn_orient_matrix_UB_32      0.0718290000
_diffrn_orient_matrix_UB_33      -0.0054660000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0725
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            28806
_diffrn_reflns_point_group_measured_fraction_full 0.934
_diffrn_reflns_point_group_measured_fraction_max 0.913
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.833
_diffrn_reflns_theta_min         4.446
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    50.579
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.18402
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    3.509
_exptl_crystal_F_000             3332
_refine_diff_density_max         2.351
_refine_diff_density_min         -1.767
_refine_diff_density_rms         0.219
_refine_ls_abs_structure_details
;
 Flack x determined using 2658 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.480(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     451
_refine_ls_number_reflns         6293
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0868
_refine_ls_R_factor_gt           0.0843
_refine_ls_shift/su_max          0.229
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1298P)^2^+68.9338P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2167
_refine_ls_wR_factor_ref         0.2221
_reflns_Friedel_coverage         0.851
_reflns_Friedel_fraction_full    0.868
_reflns_Friedel_fraction_max     0.840
_reflns_number_gt                6175
_reflns_number_total             6293
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc05188e2.cif
_cod_data_source_block           cmrv-rs-py_cu_autored
_cod_depositor_comments
'Adding full bibliography for 1568218--1568220.cif.'
_cod_database_code               1568220
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H N O Pd'
_reflns_odcompleteness_completeness 98.39
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     72.68
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C00L(H00L), C015(H015), C01A(H01I), C01E(H01L)
2.b Secondary CH2 refined with riding coordinates:
 C00U(H00A,H00B), C018(H01E,H01F), C019(H01G,H01H), C01B(H01A,H01B), C01C(H01C,
 H01D), C01D(H01J,H01K)
2.c Aromatic/amide H refined with riding coordinates:
 C00D(H00D), C00E(H00E), C00G(H00G), C00I(H00I), C00J(H00J), C00M(H00M),
 C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T),
 C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C011(H011), C012(H012),
 C013(H013), C014(H014), C016(H016), C017(H017)
;
_shelx_res_checksum              62693
_shelx_hkl_checksum              37072
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 3.103
_oxdiff_exptl_absorpt_empirical_full_min 0.351