Facile and efficient synthesis of γ-lactone and butenolide derivatives

Article abstract of DOI:10.1080/00397911.2010.527421

An efficient Baeyer-Villiger rearrangement of cyclobutanone derivatives was investigated. One-pot synthesis of keto-δ-lactone from the Baeyer-Villiger rearrangement products was developed. Meanwhile, the synthetic useful γ-lactone and butenolide derivatives could be easily prepared. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397911.2010.527421

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Facile and Efficient Synthesis of γ-
Lactone and Butenolide Derivatives
Xingxian Zhang a , Jincai Guo a & Shenghui Hu a
a College of Pharmaceutical Sciences, Zhejiang University of
Technology, Hangzhou, Zhejiang, China
Accepted author version posted online: 28 Nov 2011.Version of
record first published: 03 Feb 2012.
To cite this article: Xingxian Zhang , Jincai Guo & Shenghui Hu (2012): Facile and Efficient Synthesis
of γ-Lactone and Butenolide Derivatives, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 42:11, 1551-1558
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Synthetic Communications1, 42: 1551–1558, 2012
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397911.2010.527421
FACILE AND EFFICIENT SYNTHESIS OF c-LACTONE
AND BUTENOLIDE DERIVATIVES
Xingxian Zhang, Jincai Guo, and Shenghui Hu
College of Pharmaceutical Sciences, Zhejiang University of Technology,
Hangzhou, Zhejiang, China
GRAPHICAL ABSTRACT
Abstract An efficient Baeyer–Villiger rearrangement of cyclobutanone derivatives was
investigated. One-pot synthesis of keto-d-lactone from the Baeyer–Villiger rearrangement
products was developed. Meanwhile, the synthetic useful c-lactone and butenolide
derivatives could be easily prepared.
Keywords Baeyer–Villiger rearrangement; butenolide; cyclobutanone; lactone
INTRODUCTION
Substituted c-lactone and butenolide ring systems are widespread in nature,
and most of them also possess interesting biological activities,[1] and could be used
as potential insectides, bactericides, fungicides, antibiotics, anticancer agents, anti-
inflammatories, and allergy inhibitors. They can serve as useful intermediates for
the synthesis of complex natural products.[2] Cyclobutanone derivatives have fre-
quently been employed as versatile synthesis intermediates.[3] The Mukaiyama aldol
adduct of 1,2-bis(trimethylsiloxy)cyclobutene (BTCB) with aldehyde or acetal could
undergo geminal acylation or reduction succinoylation to provide 1,3-cyclopentane-
dione or c-keto acid under acid catalysis.[4] We recently reported an approach to
preparation of a-hydroxyl cyclobutanones by addition of aldehydes with BTCB cat-
alyzed by MgI2 etherate.[5] Herein, we describe a novel method for the synthesis of c-
lactone, keto-d-lactone, and butenolide derivatives via Baeyer–Villiger rearrange-
ment of cyclobutanones.
First, we screened the Baeyer–Villiger rearrangement conditions of cyclobuta-
none 1b prepared from piperonal as a model reaction (Table 1, entry 2). The reaction
Received February 4, 2010.
Address correspondence to Xingxian Zhang, College of Phamaceutial Sciences, Zhejiang
University of Technology, Hangzhou, Zhejiang 310032, China. E-mail: zhangxx@zjut.edu.cn
1551

1552
X. ZHANG, J. GUO, AND S. HU
Table 1. Baeyer–Villiger rearrangement of cyclobutanone derivatives
Entry
R
Rt (h)
Product
Yield (%)a
1
2
3
4
5
6
7
8
Ph
3,4-(CH2(O)2)Ph
=
trans-PhCH CH
10
6
2a
2b
2c
2d
2e
2f
82 (dr 3:2)
80 (dr 1:1)
93 (dr 3:2)
79 (dr 7:3)
82 (dr 7:3)
76b
3
4-MeOPh
2,5-(MeO)2Ph
2-ClPh
8
4
6
4-NO2Ph
a-napthyl
6
2g
2h
77 (dr 3:2)
60b
8
aisolated overall yield; ratio of diastereoselectivity of product was determined by 1H NMR analysis.
bdr not determined.
proceeded very sluggishly in the presence of mCPBA in CHCl3. Treatment of cyclo-
butanone 1b with 30% H2O2 in basic conditions gave poor yield, and the desilylation
of cyclobutanone was observed. Gratifyingly, excellent conversion and good yield
were afforded by using freshly prepared peracetic acid with sodium acetate in reflux-
ing CHCl3. Encouraged by this result, we explored Baeyer–Villiger rearrangement of
other cyclobutanones. The results are summaried in Table 1. As shown in Table 1,
all cyclobutanones provided the corresponding c-lactone in good yields with the
treatment of peracetic acid and sodium acetate.
The Baeyer–Villiger rearrangement products 2a–2c were treated with catalytic
amounts of p-TsOH in refluxing benzene, respectively. The corresponding keto-d-
lactone 3a–3c in situ afforded 74–86% yield (Scheme 1).
Reduction of keto-d-lactone 3c with NaBH4 in tetrahydrofuran (THF)
afforded the rearranged diastereomeric c-lactone in 90% yield in a ratio of
60:40,[6] which was separated by silica-gel chromatography. The structures of 4a
and 4b were assigned as syn (or threo) and anti (or erythro) respectively based on
1
their characteristic infrared (IR) and H NMR spectroscopic data.[7] Treatment of
c-lactones 5a and 5b with lithium diisopropylanaide (LDA) and PhSeCl, followed
Scheme 1. Synthesis of keto-d-lactone from c-lactone.

c-LACTONE AND BUTENOLIDE DERIVATIVES
1553
Scheme 2. An approach to synthesis of butenolide derivatives.
by addition of 30% H2O2,[8] afforded the corresponding butenolide 6a and 6b in 65%
overall yield, which provided another protocol to synthesize butenolide derivativres
(Scheme 2).
In conclusion, we have developed a facile and efficient synthesis of c-lactone,
keto-d-lactone, and butenolide derivatives from Baeyer–Villiger rearrangement pro-
ducts of cyclobutanones. The application of Baeyer–Villiger rearrangement of cyclo-
butanones into the total synthesis of natural products stryllactone will be reported in
due course.
EXPERIMENTAL
For product purification by flash column chromatography, silica gel (200–300
mesh) and light petroleum ether (PE, bp 60–90 ꢀC) are used. IR spectra were
recorded on a Nicolet FT-170SX spectrometer as liquid film. 1H and 13C NMR spec-
tra were taken on a Bruker AM-200 or AM-400 spectrometer with tetramethylsilane
(TMS) as an internal standard and CDCl3 as solvent. Electron impact–mass
Spectrometry (EI-MS) was determined on a HP-5988 spectrometer. High-resolution
mass spectra (HRMS) were determined on a Bruker Daltonics APEXII 47e FT-ICR
spectrometer.
Baeyer–Villiger Rearrangement of Cyclobutanones
NaOAc (108 mg, 1.23 mmol) was added to a solution of 2-trimethylsiloxy-2-
(1-trimethylsiloxyphenyl)-cyclobutanone 1a (149 mg, 0.44 mmol) in CHCl3(5 mL).
Stirring vigrously, 1.0 mL of freshly prepared peracetic acid was added dropwise.

1554
X. ZHANG, J. GUO, AND S. HU
After refluxing at 70 ꢀC for 10.0 h, the reaction mixture was cooled to room tempera-
ture and neutralized with NaHCO3 solid powder. The resultant was extracted with
diethyl ether (3 ꢁ 40 mL), washed with water and brine, and dried over MgSO4.
The crude product was purified by flash chromatography on silica gel to afford the
desired product 2a (126 mg) in 82% yield as a mixture of unseparated diastereomers
1
(dr: 3:2) from H NMR analysis.
1
Compound 2a. IR (film) n (cmꢂ1) 1789 (s). H NMR (CDCl3): d ¼ 0.06 (s,
9H), 0.20 (s, 9H), 1.56–2.63 (m, 1H), 2.39–2.63 (m, 3H), 4.64 (s, 0.4H) and 4.71
(s, 0.6H), 7.25–7.52 (m, 5H). EIMS: m=z 352 ([M]þ, 0.1), 337 (1), 308 (0.7), 280
(2), 205 (7), 173 (100), 73 (49). HRMS (ESI) Calcd. for C17H29O4Si2: 353.1599;
found for [M þ H]þ: 353.1593.
1
Compound 2b. IR (film) n (cmꢂ1) 1786 (s). H NMR (CDCl3): d ¼ 0.03–0.20
(m, 18H), 1.60–2.62 (m, 4H), 4.51 (s, 0.5H) and 4.67 (s, 0.5H), 6.0 (s, 2H), 6.75–6.90
(m, 3H). EIMS: m=z 396 ([M]þ, 0.8), 381 (2), 352 (0.4), 324 (3), 223 (66), 173 (100), 73
(87). HRMS (ESI) calcd. for C18H29O6Si2: 397.1497, found for [M þ H]þ: 397.1490.
1
Compuond 2c. IR (film) n (cmꢂ1) 1788 (s). H NMR (CDCl3): d ¼ 0.15 (s,
9H), 0.18 (s, 9H), 1.76–1.84 (m, 1H), 2.50–2.64 (m, 3H), 4.42 (d, J ¼ 4.0 Hz, 0.4H)
and 4.28 (d, J ¼ 8.0 Hz, 0.6H), 6.29 (dd, J ¼ 16.0 and 4.0 Hz, 1H), 3.69 (d, J ¼ 16 Hz,
1H), 7.25–7.42 (m, 5H; EIMS: m=z 378 ([M]þ, 0.1), 363 (0.3), 306 (0.3), 231 (2),
205 (12), 173 (100), 73 (90). HRMS (ESI) calcd. for C19H31O4Si2: 379.1755, found
for [M þ H]þ: 379.1757.
1
Compound 2d. IR (film) n (cmꢂ1) 1784 (s). H NMR (CDCl3): d ¼ ꢂ0.04 (s,
9H), 0.02 (s, 9H), 1.99–2.09 (m, 1H), 2.37–2.63 (m, 3H), 3.80 (s, 3H), 4.59 (s, 0.7H)
and 4.71 (s, 0.3H), 6.80-6.88 (m, 2H), 7.26–7.34 (m, 2H). EIMS: m=z 382 ([M]þ, 0.5),
367 (12), 338 (12), 209 (80), 173 (77), 73 (100). HRMS (ESI) calcd. for C18H31O5Si2:
383.1704; found for [M þ H]þ: 383.1696.
Compound 2e. IR (film) n (cmꢂ1) 1785 (s).1H NMR (CDCl3): d ¼ 0.02 (s,
9H), 0.12 (s, 9H), 1.63–1.77 (m, 1H), 2.45–2.80 (m, 3H), 3.73 (s, 3H), 3.76 (s, 3H),
5.22 (s, 0.3H) and 5.27 (s, 0.7H), 6.71–6.76 (m, 2H), 7.30 (m, 1H). EIMS: m=z 412
([M]þ, 0.5), 397 (0.4), 368 (0.2), 340 (0.8), 239 (46), 173 (38), 73 (100). HRMS
(ESI) calcd. for C19H33O6Si2: 413.1810; found for [M þ H]þ: 413.1805.
Compound 2f. IR (film) n (cmꢂ1) 1789 (s). 1H NMR (CDCl3): d ¼ 05 (s, 9H),
0.14 (s, 9H), 1.68–1.83 (m, 1H), 2.55–2.87 (m, 3H), 5.32 (s, 1H), 7.18–7.61 (m, 4H).
EIMS: m=z 373 ([M þ 2]þꢂ15, 0.3), 371 ([M]þꢂ15, 0.7), 241 (3), 239 (7), 213 (10),
173 (100). HRMS (ESI) calcd. for C17H28ClO4Si2: 387.1209; found for [MþH]þ:
387.1203.
1
Compound 2g. IR (film) n (cmꢂ1) 1787 (s). H NMR (CDCl3): d ¼ 0.07 (s,
9H), 0.17 (s, 9H), 1.53–1.60 (m, 1H), 2.45–2.62 (m, 3H), 4.68 (s, 0.4H) and 4.79
(s, 0.6H), 7.50–7.59 (m, 2H), 8.11–8.17 (m, 2H). EIMS: m=z 382 ([M]þꢂ15, 0.8),
353 (0.5), 297 (11), 250 (9), 173 (42), 73 (100). HRMS (ESI) calcd. for C17H28NO6Si2:
398.1450; found for [M þ H]þ: 398.1445.
1
Compound 2h. IR (film) n (cmꢂ1) 1788 (s). H NMR (CDCl3): d ¼ 0.01 (s,
9H), 0.05 (s, 9H), 1.58–1.74 (m, 1H), 2.59–2.96 (m, 3H), 5.69 (s, 0.4H), 7.47–7.53

c-LACTONE AND BUTENOLIDE DERIVATIVES
1555
(m, 3H), 7.75–7.84 (m, 3) 8.21–8.26 (m, 1H); EIMS: m=z 402 ([M]þ, 1), 387 (2), 358
(0.5), 330 (2), 229 (43), 173 (100), 73 (26). HRMS (ESI) calcd. for C21H31O4Si2:
403.1756; found for [MþH]þ: 403.1749.
Representative One-Pot Lactonization of Baeyer–Villiger
Rearrangement Products
The compound 2b (58 mg, 0.15 mmol) was dissolved in benzene (5 mL), fol-
lowed by addition of 20 mol% of p-TsOH. After the reaction mixture was refluxed
at 82–84 ꢀC for 8 h, it was cooled to room temperature and diluted with EtOAc
(30 mL). The organic layer was washed with water and brine and dried over MgSO4.
The crude product was purified by flash chromatography on silica gel to afford
c-lactone 3b (40 mg) in 86% yield.
1
Compound 3a. Yield. 80% IR (film) n (cmꢂ1) 1784 (s), 1736 (s). H NMR
(CDCl3): d ¼ 2.60–2.98 (m, 4H), 5.65 (s, 1H), 7.34 (br s, 5H). EIMS m=z 190
([M]þ, 33), 162 (66), 122 (27), 107 (38), 105 (100), 77 (45). HRMS (ESI) calcd. for
C11H11O3; 191.0703; found for [M þ H]þ: 191.0769.
1
Compound 3b. Yield. 86% IR (film) n (cmꢂ1) 1757 (s), 1736 (s). H NMR
(CDCl3): d ¼ 2.75–2.95 (m, 4H), 5.59 (s, 1H), 5.99 (s, 2H), 6.82 (br s, 3H). EIMS
m=z 234 ([M]þ, 38), 206 (50), 162 (13), 151 (100). HRMS (ESI) calcd. for
C12H11O5: 235.0601; found for [M þ H]þ: 235.0598.
1
Compound 3c. Yield. 74% IR (film) n (cmꢂ1) 1759 (s), 1737 (s). H NMR
(CDCl3): d ¼ 2.75–2.87 (m, 4H), 2.93–3.61 (m, 2H), 5.36 (dd, J ¼ 4.8 and 1.6 Hz,
1H), 6.25 (dd, J ¼ 16.0 and 4.8 Hz, 1H), 6.76 (dd, J ¼ 16.0 and 1.6 Hz, 1H),
7.30–7.44 (m, 5H). EIMS m=z 216 ([M]þ, 8), 188 (9), 131 (100), 115 (43), 77 (78).
HRMS (ESI) calcd. for C13H13O3: 217.0859; found for [M þ H]þ: 217.0852.
5-(1-Hydroxy-3-phenyl-allyl)-dihydro-furan-2-one (4)
The compound 3c (40 mg, 0.19 mmol) was dissolved in 2 mL of THF. NaBH4
(4 mg, 0.1 mmol) was added at ꢂ10 ꢀC, and the reaction was stirred at 0 ꢀC for
30 min. The reaction mixture was quenched with water and extracted with EtOAc.
The organic layer was washed with water and brine and dried (MgSO4). After
removal of solvent, the residue was purified by flash chromatography on silica gel
to give compound 4a (23 mg) and 4b (15 mg) in 90% overall yield.
1
Compound 4a. (60%, syn or threo) IR (film) n (cmꢂ1) 3409 (s), 1767 (s). H
NMR (CDCl3): d ¼ 15–2.35 (m, 2H), 2.50–2.70 (m, 2H), 4.33 (t, J ¼ 6.2 Hz, 1H),
4.57 (m, 1H), 6.24 (dd, J ¼ 16 and 6.8 Hz, 1H), 6.74 (d, J ¼ 16 Hz, 1H), 7.20–7.40
(m, 5H). EIMS m=z 218 ([M]þ, 2), 200 (1), 133 (100). HRMS (ESI) calcd. for
C13H14O3Na: 241.0835; found for [M þ Na]þ: 241.0834.
Compound 4b. (40%, anti or erythro) IR (film) n (cmꢂ1) 3423 (s), 1766 (s). 1H
NMR (CDCl3): d ¼ 2.15–2.20 (m, 1H), 2.25–2.35 (m, 1H), 2.45–2.55 (m, 1H),
2.60–2.70 (m, 1H), 2.98 (br s, 1H), 4.55–4.70 (m, 2H), 6.13 (dd, J ¼ 16 and 5.6 Hz,
1H), 6.76 (d, J ¼ 16 Hz, 1H), 7.20–7.45 (m, 5H). EIMS m=z 218 ([M]þ, 2), 200

1556
X. ZHANG, J. GUO, AND S. HU
(0.71), 133 (100). HRMS (ESI) calcd. for C13H14O3Na: 241.0835; found for
[M þ Na]þ: 241.0829.
syn-5-[1-(tert-Butyldimethylsilyloxy)-3-phenyl-allyl]-dihydrofuran-
2-one (5)
To a solution of compound 4a (20 mg, 0.092 mmol) in 1 mL of DMF were
added 13 mg (0.11 mmol) of 2,2-dimethylbutyl chloride and 10 mg (0.15 mmol) of
imidazole. After stirring at room temperature for 6.0 h, the reaction mixture was
diluted with diethyl ether (30 mL). The organic layer was washed with water and
brine and then dried over MgSO4. The crude product was purified by flash chroma-
tography on silica gel to give the compound 5a (27 mg, 88%) as colorless viscous oil,
IR (film) n (cmꢂ1) 1776 (s); 1H NMR (CDCl3): d ¼ 0.08 (s, 3H), 0.12 (s, 3H), 0.92 (s,
9H), 2.15–2.27 (m, 2H), 2.47–2.56 (m, 2H), 4.40–4.43 (m, 1H), 4.52–4.57 (m, 1H),
6.23 (dd, J ¼ 16.0 and 6.8 Hz, 1H), 6.64 (d, J ¼ 16.0 Hz, 1H), 7.26–7.41 (m, 5H);
13C NMR (CDCl3): d ¼ 177.3, 136.3, 132.5, 128.7, 128.0, 127.2, 126.6, 82.7, 75.1,
28.2, 25.8, 23.0, 18.1, ꢂ4.3, ꢂ4.8; EIMS m=z 317 ([M]þꢂ15, 0.3), 275 (8), 257 (9),
247 (42), 141 (38), 84 (100); HRMS (ESI) calcd. for C19H29O3Si: 333.1880; found
for [M þ H]þ: 333.1878.
anti-5-[1-(tert-Butyldimethylsilyloxy)-3-phenyl-allyl]-dihydro-furan-2-one
(5b). (85%, anti or erythro) 1H NMR (CDCl3): d ¼ 0.09 (s, 3H), 0.12 (s, 3H), 0.94 (s,
9H), 2.08–2.14 (m, 1H), 2.31–2.37 (m, 1H), 2.45–2.51 (m, 1H), 2.57–2.66 (m, 1H),
4.54–4.58 (m, 1H), 4.65–4.67 (m, 1H), 6.10 (dd, J ¼ 16.0 and 5.6 Hz, 1H), 6.70 (d,
J ¼ 16.0 Hz, 1H), 7.25–7.41 (m, 5H). 13C NMR (CDCl3): d ¼ 177.5, 136.2, 132.2,
128.7, 128.0, 127.1, 126.5, 82.2, 73.9, 28.6, 25.8, 20.6, 18.1, ꢂ4.6, ꢂ4.9; EIMS m=z
317([M]þꢂ15, 0.2), 275 (15), 257 (12), 247 (47), 141 (52), 73 (100). HRMS (ESI)
calcd. for C19H29O3Si: 333.1880; found for [M þ H]þ: 333.1871.
syn-5-[1-(tert-Butyldimethylsilyloxy)-3-phenyl-allyl]-5H-furan-2-one
(6)
To a solution of diisopropyl amine (39 mg, 0.39 mmol) in 1 mL of anhydrous
THF was added dropwise 0.25 mL of n-BuLi (0.39 mmol, 1.6 M) at 0 ꢀC under
argon. After addition, the reaction mixture was stirred at 0 ꢀC for 15 min. The freshly
prepared LDA solution was cooled to ꢂ78 ꢀC, and 107 mg (0.32 mmol) of compound
5a in 2 mL of THF was introduced. The reaction mixture continued to be stirred at ꢂ
78 ꢀC, for 30 min, followed by addition of PhSeCl (74 mg, 0.39 mmol) in 1 mL of
THF. The reaction was allowed to warm to room temperature, quenched with water,
extracted with diethyl ether, washed with water and brine, and concentrated. The
residue was dissolved in 2 mL of THF, followed by addition of 0.1 mL of 30%
H2O2. The reaction was stirred for 0.5 h, extracted with diethyl ether, and dried over
MgSO4. The crude product was purified by flash chromatography on silica gel to
afford 12 mg of compound 6a (65%) as a colorless viscous oil. IR (film) n (cmꢂ1
)
1
1778 (s), 1758 (s). H NMR (CDCl3): d ¼ 0.08 (s, 3H), 0.11 (s, 3H), 0.92 (s, 9H),
4.57 (t, J ¼ 5.8 Hz, 1H), 5.05 (m, 1H), 6.03 (dd, J ¼ 16.0 and 6.3 Hz, 1H), 6.16 (dd,
J ¼ 5.8 and 1.8 Hz, 1H), 6.61 (d, J ¼ 16.0 Hz, 1H), 7.20–7.40 (m, 5H), 7.50 (dd,

c-LACTONE AND BUTENOLIDE DERIVATIVES
1557
J ¼ 5.8 and 1.4 Hz, 1H). EIMS m=z 315 ([M]þꢂ15, 0.1), 273 (2), 247 (26), 113 (18), 73
(100). HRMS (ESI) calcd. for C19H27O3Si: 331.1724; found for [MþH]þ: 331.1719.
anti-5-[1-(tert-Butyldimethylsilyloxy)-3-phenyl-allyl]-5H-furan-2-one (6b).
(60%, anti or erythro) IR (film) n (cmꢂ1) 789 (s), 1758 (s). 1H NMR (CDCl3): d ¼ 0.06
(s, 3H), 0.09 (s, 3H), 0.89 (s, 9H), 4.61 (m, 1H), 5.00 (m, 1H), 6.19 (dd, J ¼ 5.8 and
2.8 Hz, 1H), 6.22 (dd, J ¼ 16 and 5.6 Hz, 1H), 6.71 (d, J ¼ 16 Hz, 1H), 7.15–7.45
(m, 5H), 7.49 (dd, J ¼ 5.8 and 1.6 Hz, 1H); EIMS m=z 315 ([M]þꢂ15, 0.1), 287
(0.8), 273 (4), 247 (34), 73 (100). HRMS (ESI) calcd. for C19H27O3Si: 331.1724;
found for [M þ H]þ: 331.1719.
ACKNOWLEDGMENTS
Financial support from the Zhejiang Province Natural Science Foundation of
China (Project Y4100692) and Zhejiang University of Technology Younger Scholars
Program are greatly appreciated.
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