PdII-Catalyzed Conjugate Addition of Boronic Acids
C-Me), 79.4 (O-CH), 68.4 (CH2-O), 47.3 (CH-CH2-CO), 45.8 (CH- 17.6 (C-CH3, anti), 17.4 (C-CH3, syn) ppm. C23H28O5 (384.47):
CH2-CO), 30.7 (COCH3), 26.9 (CH3), 25.8 (CH3) ppm. C15H20O3
calcd. C 71.85, H 7.34; found C 71.98, H 7.45.
(248.32): calcd. C 72.55, H 8.12; found C 72.51, H 8.20.
(2S,3R)-5-Oxo-3,5-diphenylpentane-1,2-diyl Dibenzoate (anti-3e)
and (2S,3S)-5-Oxo-3,5-diphenylpentane-1,2-diyl Dibenzoate (syn-
3e): Yield 40.0 mg (77 %); anti-3e/syn-3e ratio 70:30. 1H NMR
(300 MHz, CDCl3): δ = 7.78–8.03 (m, 5 H, ArH), 7.20–7.61 (m, 15
H, ArH), 5.94 (dt, J = 7.4, 4.3 Hz, 1 H, O-CH syn), 5.81 (ddd, J
= 10.2, 6.1, 2.8 Hz, 1 H, O-CH anti), 4.47 (dd, J = 12.0, 2.8 Hz, 1
H, OCH2), 4.34 (dd, J = 12.0, 8.5 Hz, 1 H, OCH2 syn), 4.21 (dd,
J = 12.0, 6.1 Hz, 1 H, OCH2 anti), 4.01–4.15 (m, 1 H CH2-COPh),
3.54 (dd, J = 6.1, 3.5 Hz, 1 H, CH-Ph anti), 3.44–3.55 (m, 3 H,
CH-Ph syn, CH2-COPh) ppm. 13C NMR (75 MHz, CDCl3): δ =
197.8 (Ph-C=O, anti), 197.5 (Ph-C=O, syn), 166.4 (O-C=O, anti),
166.2 (O-C=O, syn), 166.2 (O-C=O, anti), 166.1 (O-C=O, syn),
140.1 (CAr, anti), 139.2 (CAr, syn), 136.9 (CAr), 133.4 (CArH), 133.3
(CArH), 133.2 (CArH), 129.9 (CArH), 129.8 (CArH), 129.8 (CArH),
129.6 (CAr, anti), 129.2 (CArH), 129.0 (CArH), 128.8 (CArH), 128.7
(CArH), 128.6 (CArH), 128.6 (CArH), 128.5 (CArH), 128.4 (CArH),
128.2 (CArH), 128.1 (CArH), 127.7 (CArH), 127.5 (CArH), 75.0 (O-
CH, anti), 73.7 (O-CH, syn), 64.7 (CH2-O, syn), 64.5 (CH2-O, anti),
42.6 (CH-CH2-CO, anti), 42.0 (CH-CH2-CO, syn), 41.7 (CH-CH2-
CO, anti), 40.8 (CH-CH2-CO, syn) ppm. C31H26O5 (478.54): calcd.
C 71.81, H 5.48; found C 77.74, H 5.51.
(S)-4-[(S)-2,2-Dimethyl-1,3-dioxolan-4-yl]-4-phenylbutan-2-one
(syn-3b): Yield 8.4 mg (11%). 1H NMR (300 MHz, CDCl3): δ =
7.10–7.27 (m, 5 H, ArH), 4.11–4.26 (m, 1 H, O-CH), 3.82 (dd, J =
8.1, 6.4 Hz, 1 H, OCH2), 3.48 (t, J = 8.1 Hz, 1 H, OCH2), 3.34–
3.42 (m, 1 H, CH-Ph), 2.79–2.93 (m, 2 H, CH2-COPh), 2.01 (s, 3
H, CO-CH3), 1.24 (s, 3 H, CH3), 1.21 (s, 3 H, CH3) ppm. 13C NMR
(75 MHz, CDCl3): δ = 207.1 (C=O), 139.9 (CAr), 129.0 (2CArH),
128.5 (2CArH), 127.2 (CArH), 109.2 (Me-C-Me), 78.2 (O-CH), 66.7
(CH2-O), 45.6 (CH-CH2-CO), 42.5 (CH-CH2-CO), 30.7 (COCH3),
26.4 (CH3), 25.5 (CH3) ppm. C15H20O3 (248.32): calcd. C 72.55, H
8.12; found C 72.53, H 8.19.
(R)-1,3-Diphenyl-3-[(S)-1,4-dioxaspiro[4.5]decan-2-yl]propan-1-one
1
(anti-3c): Yield 36.0 mg (70%). H NMR (300 MHz, CDCl3): δ =
7.88–7.97 (m, 2 H, ArH), 7.48–7.56 (m, 1 H, ArH), 7.37–7.47 (m,
2 H, ArH), 7.14–7.32 (m, 5 H, ArH), 4.32 (dt, J = 9.0, 6.3 Hz, 1
H, O-CH), 3.67–3.80 (m, 2 H, OCH2, CH2-COPh), 3.60 (dd, J =
8.5, 6.3 Hz, 1 H, OCH2), 3.33–3.53 (m, 2 H, CH-Ph, CH2-COPh),
1.49–1.71 (m, 8 H, 4CH2), 1.31–1.46 (m, 2 H, CH2) ppm. 13C NMR
(75 MHz, CDCl3): δ = 198.7 (C=O), 141.2 (CAr), 137.3 (CAr), 132.9
(CArH), 128.7 (2CArH), 128.6 (2CArH), 128.2 (4CArH), 127.1 (CArH),
110.3 (CH2-C-CH2), 79.0 (O-CH), 68.2 (CH2-O), 46.1 (CH-CH2-
CO), 42.5 (CH-CH2-CO), 36.6 (CH2), 35.3 (CH2), 25.3 (CH2), 24.1
(CH2), 24.0 (CH2) ppm. C23H26O3 (350.45): calcd. C 78.83, H 7.48;
found C 78.99, H 7.45.
(S,E)-5-[(S)-2,2-Dimethyl-1,3-dioxolan-4-yl]-1,3-diphenylpent-4-en-
1-one (anti-3f) and (R,E)-5-[(S)-2,2-Dimethyl-1,3-dioxolan-4-yl]-1,3-
diphenylpent-4-en-1-one (syn-3f): Yield 45.9 mg (88%); anti-3f/syn-
1
3f ratio 50:50. H NMR (300 MHz, C6D6): δ = 7.65–7.76 (m, 2 H,
ArH), 6.91–7.22 (m, 8 H, ArH), 5.88 (dt, J = 15.5, 6.8 Hz, 1 H, O-
CH-CH=CH), 5.44 (dd, J = 15.5, 7.1 Hz, 1 H, O-CH-CH=CH),
4.30 (q, J = 6.8 Hz, 1 H, O-CH), 4.14–4.25 (m, 1 H, CH-Ph), 3.70–
3.78 (m, 1 H, OCH2), 3.36 (td, J = 7.9, 2.3 Hz, 1 H, OCH2), 3.03
(t, J = 7.5 Hz, 2 H, CH2-COPh), 1.39 (s, 3 H, CH3), 1.36 (s, 3 H,
CH3), 1.34 (s, 3 H, CH3), 1.33 (s, 3 H, CH3) ppm. 13C NMR
(75 MHz, C6D6): δ = 197.0 (Ph-C=O), 197.0 (Ph-C=O), 143.7
(CAr), 143.4 (CAr), 137.7 (CAr), 136.6 (O-CH-CH=CH), 136.6 (O-
CH-CH=CH), 132.8 (CArH), 132.7 (CArH), 129.0 (CArH), 128.9
(CArH), 128.8 (2CArH), 128.6 (2CArH), 128.6 (2CArH), 126.8 (CArH),
126.8 (CArH), 109.3 (Me-C-Me), 77.2 (O-CH), 77.2 (O-CH), 69.7
(CH2-O), 69.7 (CH2-O), 44.4 (CH-CH2-CO), 44.3 (CH-CH2-CO),
43.6 (CH-CH2-CO), 43.5 (CH-CH2-CO), 27.0 (C-CH3), 26.2 (C-
CH3) ppm. C22H24O3 (336.42): calcd. C 78.54, H 7.19; found C
78.74, H 7.26.
(S)-1,3-Diphenyl-3-[(S)-1,4-dioxaspiro[4.5]decan-2-yl]propan-1-one
(syn-3c): Yield 4.0 mg (8%). 1H NMR (300 MHz, CDCl3): δ =
7.92–7.98 (m, 2 H, ArH), 7.50–7.58 (m, 1 H, ArH), 7.40–7.48 (m,
2 H, ArH), 7.16–7.33 (m, 5 H, ArH), 4.39 (ddd, J = 10.4, 6.2,
4.1 Hz, 1 H, O-CH), 3.93 (dd, J = 8.2, 6.2 Hz, 1 H, OCH2), 3.62–
3.71 (m, 1 H, CH2-COPh), 3.50–3.61 (m, 2 H, OCH2, CH-Ph),
3.44 (dd, J = 17.0, 7.7 Hz, 1 H, CH2-COPh), 1.29–1.60 (m, 10 H,
5CH2) ppm. 13C NMR (75 MHz, CDCl3): δ = 198.6 (C=O), 140.2
(2CAr), 133.2 (CArH), 129.2 (2CArH), 128.7 (2CArH), 128.3 (2CArH),
128.3 (2CArH), 127.0 (CArH), 109.7 (CH2-C-CH2), 77.8 (O-CH),
66.4 (CH2-O), 42.6 (CH-CH2-CO), 40.8 (CH-CH2-CO), 36.1
(CH2), 35.2 (CH2), 25.3 (CH2), 24.1 (CH2), 24.0 (CH2) ppm.
C23H26O3 (350.45): calcd. C 78.83, H 7.48; found C 78.97, H 7.44.
(R)-3-[(2S,5R,6R)-5,6-Dimethoxy-5,6-dimethyl-1,4-dioxan-2-yl]-1,3-
diphenylpropan-1-one (anti-3d) and (S)-3-[(2S,5R,6R)-5,6-Dimeth-
oxy-5,6-dimethyl-1,4-dioxan-2-yl]-1,3-diphenylpropan-1-one (syn-
3d): Yield 47.5 mg (95%); anti-3d/syn-3d ratio 85:15. 1H NMR
(300 MHz, CDCl3): δ = 7.87–7.93 (m, 2 H, ArH), 7.50–7.58 (m, 1
H, ArH), 7.39–7.49 (m, 2 H, ArH), 7.14–7.33 (m, 5 H, ArH), 4.05–
4.16 (m, 1 H, O-CH), 3.81 (dd, J = 16.4, 4.0 Hz, 1 H, OCH2), 3.42–
3.62 (m, 2 H, CH2-COPh, OCH2), 3.35 (s, 3 H, OCH3, anti), 3.28
(dd, J = 16.4, 6.9 Hz, 1 H, CH2-COPh), 3.25 (s, 3 H, OCH3, anti),
3.18 (s, 3 H, OCH3, syn), 3.09 (dd, J = 11.4, 3.0 Hz, 1 H, CH-Ph),
3.06 (s, 3 H, OCH3, syn), 1.32 (s, 3 H, C-CH3), 1.29 (s, 3 H, C-
CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 198.6 (C=O, anti),
Methyl (R)-3-[(S)-2,2-Dimethyl-1,3-dioxolan-4-yl]-3-phenylpropano-
1
ate (anti-6a): Yield 45.0 mg (79%). H NMR (300 MHz, CDCl3):
δ = 7.05–7.27 (m, 5 H, ArH), 4.15 (dt, J = 9.3, 6.1 Hz, 1 H, O-
CH), 3.66 (dd, J = 8.5, 6.1 Hz, 1 H, OCH2), 3.49 (dd, J = 8.5,
6.1 Hz, 1 H, OCH2), 3.47 (s, 3 H, COO-CH3), 3.14 (td, J = 9.3,
4.9 Hz, 1 H, CH-Ph), 2.96 (dd, J = 15.5, 4.9 Hz, 1 H, CH2-COPh),
2.58 (dd, J = 15.5, 9.3 Hz, 1 H, CH2-COPh), 1.37 (s, 3 H, C-CH3),
1.28 (s, 3 H, C-CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 172.7
(C=O), 140.4 (CAr), 128.8 (2CArH), 128.1 (2CArH), 127.4 (CArH),
109.8 (Me-C-Me), 79.2 (O-CH), 68.4 (CH2-O), 51.6 (OCH3), 46.8
(CH-CH2-CO), 38.3 (CH2-CO), 27.0 (C-CH3), 25.8 (C-CH3) ppm.
C15H20O4 (264.32): calcd. C 68.16, H 7.63; found C 68.25, H 7.70.
198.4 (C=O, syn), 141.2 (CAr, syn), 140.3 (CAr, anti), 137.4 (CAr
,
anti), 137.2 (CAr, syn), 133.1 (CArH, syn), 132.9 (CArH, anti), 128.7 Methyl (S)-3-[(S)-2,2-Dimethyl-1,3-dioxolan-4-yl]-3-phenylpropano-
1
(2CArH, syn), 128.4 (2CArH, anti), 128.6 (2CArH), 128.2 (2CArH), ate (syn-6a): Yield 5.0 mg (9%). H NMR (300 MHz, CDCl3): δ =
128.2 (2CArH, syn), 128.1 (2CArH, anti),127.2 (CArH, anti), 126.7 7.10–7.27 (m, 5 H, ArH), 4.22–4.31 (m, 1 H, O-CH), 3.83 (dd, J =
(CArH, syn), 99.6 (O-C- CH3, anti), 99.4 (O-C- CH3, syn), 97.9 (O-
8.2, 6.4 Hz, 1 H, OCH2), 3.52 (s, 3 H, COO-CH3), 3.46–3.54 (m, 1
C- CH3), 70.2 (O-CH, anti), 69.7 (O-CH, syn), 62.7 (CH2-O, anti), H, OCH2), 3.29–3.40 (m, 1 H, CH-Ph), 2.77 (dd, J = 15.7, 6.2 Hz,
61.8 (CH2-O, syn), 48.2 (OCH3, anti), 48.1 (OCH3, anti), 47.9 1 H, CH2-COPh), 2.66 (dd, J = 15.7, 8.7 Hz, 1 H, CH2-COPh),
(OCH3, syn), 43.6 (CH-CH2-CO, anti), 42.2 (CH-CH2-CO, syn), 1.24 (s, 3 H, C-CH3), 1.22 (s, 3 H, C-CH3) ppm. 13C NMR
41.4 (CH-CH2-CO, anti), 41.0 (CH-CH2-CO, syn), 17.9 (C-CH3), (75 MHz, CDCl3): δ = 172.6 (C=O), 139.6 (CAr), 128.7 (2CArH),
Eur. J. Org. Chem. 2015, 1754–1763
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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