Synthesis of 6β-Hydroxy-5,5,8aβ-trimethyloctahydronaphthalen-1(2H)-one Toward the Establishment of the Scaffold of Phenylspirodrimane Meroterpenoid Natural Products †

doi:10.7503/cjcu20190639

Abstract

Abstract:

Starting from ethyl(E)-5,9-dimethyldeca-4,8-dienoate, we developed a method for the synthesis of 6β-hydroxy-5,5,8aβ-trimethyloctahydronaphthalen-1-one(1), which was successfully applied to the establishment of the skeleton of phenylspirodrimane meroterpenoid natural products. Key steps such as regioselective epoxidation and Cp₂TiCl-promoted radical cascade cyclization have been optimized. The structures of the compounds synthesized have been characterized with nuclear magnetic resonance spectroscopy(NMR) and high resolution mass spectrometry(HRMS).

Key words: 6β-Hydroxy-5,5,8aβ-trimethyloctahydronaphthalen-1(2H)-one, Phenylspirodrimanes meroterpenoids, Epoxidation, Free radical tandem cyclization

CLC Number:

O624.3

TrendMD:

HU Zhiyuan, WAN Qiuxiang, ZHOU Hang, SONG Chuanjun, CHANG Junbiao. Synthesis of 6β-Hydroxy-5,5,8aβ-trimethyloctahydronaphthalen-1(2H)-one Toward the Establishment of the Scaffold of Phenylspirodrimane Meroterpenoid Natural Products ^†[J]. Chem. J. Chinese Universities, 2020, 41(5): 955.

Figures/Tables 6

References 28

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Compd.	Appearance	Yield(%)	HRMS, m/z[M+H]⁺
1	Light brown oil	51	211.1690
4	Light brown oil	90
5	Brown oil	95
6	Light brown oil	85	192.1746
7	Light brown oil	69	208.1699
11	White solid	48	531.3499
12	White solid	81	531.3501

Compd.	Appearance	Yield(%)	HRMS, m/z[M+H]⁺
1	Light brown oil	51	211.1690
4	Light brown oil	90
5	Brown oil	95
6	Light brown oil	85	192.1746
7	Light brown oil	69	208.1699
11	White solid	48	531.3499
12	White solid	81	531.3501

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(100 MHz, CDCl₃), δ
1	3.21—3.07(m, 1H), 2.56(td, J=14.0, 7.2 Hz, 1H), 2.22—2.17(m, 1H), 2.10—2.03(m, 1H), 1.76—1.51(m, 8H), 1.14(s, 3H), 1.01(s, 3H), 0.89(s, 3H)	215.5, 78.1, 52.6, 48.6, 39.7, 37.4, 31.2, 28.0, 26.9, 26.2, 20.7, 18.6, 15.8
4	5.14(t, J=7.2 Hz, 1H), 5.08(t, J=6.8 Hz, 1H), 3.63(t, J=6.4 Hz, 2H), 2.10—1.96(m, 8H), 1.67(s, 3H), 1.61(s, 3H), 1.59(s, 3H)	135.8, 131.4, 124.2, 123.7, 62.7, 39.7, 32.7, 26.6, 25.7, 24.2, 17.7, 15.9
5	5.09—5.08(m, 2H), 3.20(t, J=7.2 Hz, 2H), 2.14—2.06(m, 4H), 2.01(t, J=7.6 Hz, 2H), 1.92—1.85(m, 2H), 1.70(s, 3H), 1.65(s, 3H), 1.62(s, 3H)	136.8, 131.4, 124.2, 122.3, 39.7, 33.6, 28.6, 26.6, 25.7, 17.7, 16.2, 6.8
6	5.06—5.01(m, 2H), 2.29(t, J=7.2 Hz, 2H), 2.16—2.11(m, 2H), 2.05(t, J=7.2 Hz, 2H), 2.00—1.97(m, 2H), 1.72—1.64(m, 5H), 1.60(s, 3H), 1.58(s, 3H)	137.6, 131.5, 124.1, 121.8, 119.8, 39.7, 26.6, 26.5, 25.7, 25.5, 17.6, 16.2, 16.0
7	5.10(t, J=7.2 Hz, 1H), 2.67(t, J=6.4 Hz, 1H), 2.31(t, J=7.2 Hz, 2H), 2.18—2.09(m, 4H), 1.69(t, J=7.2 Hz, 2H), 1.63—1.59(m, 5H), 1.28(s, 3H), 1.24(s, 3H)	136.7, 122.3, 119.7, 64.0, 58.2, 36.4, 27.3, 26.7, 25.4, 24.2, 18.7, 16.4, 16.1
11	11.78(s, 1H), 7.89(s, 1H), 3.93(s, 3H), 3.58—3.42(m, 2H), 3.19(dd, J=14.8 Hz, 6.8 Hz, 1H), 2.42(s, 3H), 2.19—2.17(m, 2H), 2.09(s, 3H), 1.75(s, 3H), 1.66(s, 1H), 1.26(s, 1H), 1.18—1.14(m, 2H), 1.04(s, 3H), 0.95(s, 3H), 0.89(s, 3H), 0.87(s, 9H), 0.79(s, 3H), 0.02—0(m, 6H)	173.0, 159.3, 159.2, 139.4, 137.4, 116.6, 109.0, 105.2, 79.0, 51.8, 50.7, 39.5, 39.3, 33.92, 33.86, 28.5, 27.8, 25.94, 25.90, 20.5, 20.0, 18.9, 18.70, 18.69, 18.1, 16.2, 11.8, -3.7, -4.9
12	3.80(s, 3H), 3.10—2.99(m, 2H), 2.65(d, J=1.6 Hz, 1H), 2.24(s, 3H), 2.00(s, 3H), 1.68—1.64(m, 1H), 1.56—1.52(m, 5H), 1.40—1.36(m, 3H), 1.07(d, J=0.4 Hz, 1H), 0.89(s, 3H), 0.85(s, 3H), 0.81—0.78(m, 12H), 0.70(s, 3H), 0.67—0.64(m, 3H), -0.05(s, 3H), -0.08(s, 3H)	167.3, 158.3, 150.4, 135.9, 112.9, 109.0, 96.1, 78.0, 50.5, 44.8, 41.1, 38.2, 35.9, 30.2, 30.1, 28.4, 27.7, 26.1, 24.9, 20.3, 17.1, 16.0, 15.1, 14.8, 14.4, 10.2, 0, -4.8, -6.0

Compd.	¹H NMR(400 MHz, CDCl₃), δ	¹³C NMR(100 MHz, CDCl₃), δ
1	3.21—3.07(m, 1H), 2.56(td, J=14.0, 7.2 Hz, 1H), 2.22—2.17(m, 1H), 2.10—2.03(m, 1H), 1.76—1.51(m, 8H), 1.14(s, 3H), 1.01(s, 3H), 0.89(s, 3H)	215.5, 78.1, 52.6, 48.6, 39.7, 37.4, 31.2, 28.0, 26.9, 26.2, 20.7, 18.6, 15.8
4	5.14(t, J=7.2 Hz, 1H), 5.08(t, J=6.8 Hz, 1H), 3.63(t, J=6.4 Hz, 2H), 2.10—1.96(m, 8H), 1.67(s, 3H), 1.61(s, 3H), 1.59(s, 3H)	135.8, 131.4, 124.2, 123.7, 62.7, 39.7, 32.7, 26.6, 25.7, 24.2, 17.7, 15.9
5	5.09—5.08(m, 2H), 3.20(t, J=7.2 Hz, 2H), 2.14—2.06(m, 4H), 2.01(t, J=7.6 Hz, 2H), 1.92—1.85(m, 2H), 1.70(s, 3H), 1.65(s, 3H), 1.62(s, 3H)	136.8, 131.4, 124.2, 122.3, 39.7, 33.6, 28.6, 26.6, 25.7, 17.7, 16.2, 6.8
6	5.06—5.01(m, 2H), 2.29(t, J=7.2 Hz, 2H), 2.16—2.11(m, 2H), 2.05(t, J=7.2 Hz, 2H), 2.00—1.97(m, 2H), 1.72—1.64(m, 5H), 1.60(s, 3H), 1.58(s, 3H)	137.6, 131.5, 124.1, 121.8, 119.8, 39.7, 26.6, 26.5, 25.7, 25.5, 17.6, 16.2, 16.0
7	5.10(t, J=7.2 Hz, 1H), 2.67(t, J=6.4 Hz, 1H), 2.31(t, J=7.2 Hz, 2H), 2.18—2.09(m, 4H), 1.69(t, J=7.2 Hz, 2H), 1.63—1.59(m, 5H), 1.28(s, 3H), 1.24(s, 3H)	136.7, 122.3, 119.7, 64.0, 58.2, 36.4, 27.3, 26.7, 25.4, 24.2, 18.7, 16.4, 16.1
11	11.78(s, 1H), 7.89(s, 1H), 3.93(s, 3H), 3.58—3.42(m, 2H), 3.19(dd, J=14.8 Hz, 6.8 Hz, 1H), 2.42(s, 3H), 2.19—2.17(m, 2H), 2.09(s, 3H), 1.75(s, 3H), 1.66(s, 1H), 1.26(s, 1H), 1.18—1.14(m, 2H), 1.04(s, 3H), 0.95(s, 3H), 0.89(s, 3H), 0.87(s, 9H), 0.79(s, 3H), 0.02—0(m, 6H)	173.0, 159.3, 159.2, 139.4, 137.4, 116.6, 109.0, 105.2, 79.0, 51.8, 50.7, 39.5, 39.3, 33.92, 33.86, 28.5, 27.8, 25.94, 25.90, 20.5, 20.0, 18.9, 18.70, 18.69, 18.1, 16.2, 11.8, -3.7, -4.9
12	3.80(s, 3H), 3.10—2.99(m, 2H), 2.65(d, J=1.6 Hz, 1H), 2.24(s, 3H), 2.00(s, 3H), 1.68—1.64(m, 1H), 1.56—1.52(m, 5H), 1.40—1.36(m, 3H), 1.07(d, J=0.4 Hz, 1H), 0.89(s, 3H), 0.85(s, 3H), 0.81—0.78(m, 12H), 0.70(s, 3H), 0.67—0.64(m, 3H), -0.05(s, 3H), -0.08(s, 3H)	167.3, 158.3, 150.4, 135.9, 112.9, 109.0, 96.1, 78.0, 50.5, 44.8, 41.1, 38.2, 35.9, 30.2, 30.1, 28.4, 27.7, 26.1, 24.9, 20.3, 17.1, 16.0, 15.1, 14.8, 14.4, 10.2, 0, -4.8, -6.0