The rhodium-catalyzed carbene cyclization cycloaddition cascade reaction of vinylsulfonates

Article abstract of DOI:10.1002/adsc.200900695

Vinylsulfonates have proved to be excellent dipolarophiles for carbonyl ylides derived from diazoketones in rhodium-catalyzed intramolecular cycloadditions. Polyfunctional substrates, such as 8 and (+)-15, were readily available from hydroxy esters, e.g. 1 and the cyclopenta-1,3-dione 10, respectively, and the resulting polycyclic sultones were formed under mild reaction conditions in high yields with very good diastereoselectivities. A ruthenium-catalyzed asymmetric transfer hydrogenation was found to desymmetrize the meso-cyclopenta-1,3-dione 12 efficiently.

Full text of DOI:10.1002/adsc.200900695

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DOI: 10.1002/adsc.200900695
The Rhodium-Catalyzed Carbene Cyclization Cycloaddition
Cascade Reaction of Vinylsulfonates
Bairu Shi,a Sandra Merten,a David K. Y. Wong,b John C. K. Chu,b Lok Lok Liu,b
Sze Kui Lam,b Anne Jꢀger,a,c Wing-Tak Wong,b,c Pauline Chiu,b,* and Peter Metza,*
a
Department of Chemistry, Organic Chemistry I, Technische Universitꢀt Dresden, Bergstr. 66, 01069 Dresden, Germany
Fax : (+49)-351-463-33162; e-mail: peter.metz@chemie.tu-dresden.de
Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug
b
Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong, Peopleꢁs Republic of China
Fax : (+852)-2857-1586; e-mail: pchiu@hku.hk
Authors responsible for X-ray diffraction analyses
c
Received: October 6, 2009
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200900695.
Abstract: Vinylsulfonates have proved to be excel-
lent dipolarophiles for carbonyl ylides derived from
diazoketones in rhodium-catalyzed intramolecular
cycloadditions. Polyfunctional substrates, such as 8
and (+)-15, were readily available from hydroxy
esters, e.g. 1 and the cyclopenta-1,3-dione 10, re-
spectively, and the resulting polycyclic sultones
were formed under mild reaction conditions in high
yields with very good diastereoselectivities. A
ruthenium-catalyzed asymmetric transfer hydroge-
nation was found to desymmetrize the meso-cyclo-
penta-1,3-dione 12 efficiently.
ketone,[12] (ꢀ)-camptothecin,[13] (ꢁ)-pseudolaric acid
A,[14] (ꢁ)-indicol,[15] and (ꢁ)-platensimycin.[16]
It should be noted that the majority of these syn-
theses employed the carbene cyclization together with
an intramolecular cycloaddition. This version of the
reaction involves regioselective cycloadditions, due to
the geometric constraints imposed by the tether. In
contrast, the intermolecular cycloaddition is often lim-
ited to reactions with symmetrical dipolarophiles such
as dimethyl acetylenedicarboxylate or strongly steri-
cally-biased substrates such as terminal alkynes; with
other dipolarophiles, poor regioselectivity and endo/
exo diastereoselectivity is often encountered.[17] The
development of novel catalysts with a range of elec-
tronic and steric characteristics to improve the selec-
tivities of the intermolecular cycloaddition is ongo-
ing,[18] but the results are not general.
Keywords: asymmetric reduction; cycloaddition;
domino reactions; sulfur heterocycles; transition
metal catalysis
One strategy by which we are attempting to address
this problem is to design and investigate an intra-
AHCTUNGTREGmNNUN olecular CCCC reaction to produce regioselectively
The carbene cyclization cycloaddition cascade and stereoselectively cycloadducts that could ulti-
(CCCC) reaction is a powerful and atom-economical mately undergo ring cleavage to afford products
reaction to yield stereochemically defined oxapolycy- which are akin to those obtained from an intermolec-
clic adducts.[1] In this one-step metal-catalyzed reac- ular cycloaddition. In this connection, we have inves-
tion, three distinct sigma bonds are forged, resulting tigated the intramolecular CCCC reaction with teth-
in the creation of up to four new stereogenic centers. ered vinylsulfonates. The vinylsulfonate is a highly re-
The utility of this reaction in the construction of com- active functional group, where the resulting sultone
plex molecular scaffolds has been demonstrated by its cycloadduct could be elaborated in various ways to
application in the formal and total syntheses of chal- eventually yield sulfur-free products.[19,20] However,
lenging natural products, including (ꢀ)-aspidophy- while vinylsulfonates have been effectively used as
tine,[2] (ꢀ)-illudin M,[3] (ꢀ)-vallesamidine,[4] (ꢀ)-lyco- Diels–Alder dienophiles,[19] they have never been in-
podine,[5] (ꢀ)-epoxysorbicillinol,[6] (ꢀ)-nemorensic vestigated as dipolarophiles for carbonyl ylide cyclo-
acid,[7] (+)-zaragozic acids A[8] and C,[9] (ꢁ)-polygalo- additions. Herein we report the successful implemen-
lides
A
and B,[10] (ꢁ)-colchicine,[11] mappicine tation of this CCCC strategy, which generates sultone
cycloadducts with excellent yields. Moreover, the re-
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The Rhodium-Catalyzed Carbene Cyclization Cycloaddition Cascade Reaction
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Scheme 1. Synthesis of vinylsulfonate 8a. Reagents and conditions: a) TBSCl, imidazole, DMF, 08C to room temperature,
100%; b) HN (CH2)3OMgCl, THF, 08C, 94%; d)
A
ACHTUNGTRENNUNG
Dess–Martin periodinane, CH2Cl2, room temperature, 82%; e) N2CHCO2Et, cat. SnCl2, CH2Cl2, room temperature, 79%; f)
TsN3, Et3N, MeCN, 08C, 79%; g) 40% aqueous HF/MeCN (5:95), room temperature, 98%; h) CH2=CHSO2Cl, cat. DMAP,
Et3N, CH2Cl2, 08C, 67%.
action also proceeds with high diastereoselectivity
and can afford optically pure cycloadducts as chiral
intermediates for organic synthesis.
The first challenge was to devise a route to sub-
strates featuring a diazoketone and a vinylsulfonate,
both of which are reactive functional groups, in the
presence of each other. These substrates 8 were ulti-
mately accessed through diazoketones 6 that were de-
protected and sulfonylated in the presence of the
diazo functionality. The overall route is exemplified
by the synthesis of 8a (Scheme 1). a-Hydroxy ester 1a
was protected and converted to the Weinreb amide
2a,[21] which was homologated using Normantꢁs
Grignard reagent[22] to give hydroxy ketone 3a. Oxi-
dation[23] to aldehyde 4a and subsequent conversion[24]
to keto ester 5a provided the substrate for diazo
transfer[25] to afford diazoketone 6a. Cleavage of the
silyl protecting group in the presence of the diazoke-
tone was successfully achieved using HF/MeCN to
give 7a. Sulfonylation finally furnished the required
substrate 8a.
By a similar sequence of reactions, a-hydroxy
esters 1b–d, as well as b-hydroxy esters 1e, f have
Scheme 2. Synthesis of vinylsulfonates 8b–h.
been homologated to afford the corresponding diazo-
ketones 8b–f (Scheme 2). Optically pure diazoketones 9e–h, respectively, in high yields and with excellent
(+)-8c and (ꢁ)-8d were prepared from the chiral al- stereoselectivities. Thus, the simple diastereoselectiv-
cohols (+)-1c and (ꢁ)-1d without racemization. Anal- ity for prochiral substrates (8a, b, e, g, h) was com-
ogously, diazoketones 8g and 8h bearing b-substituted plete, and the substrate-induced diastereoselectivity
vinylsulfonates were derived from 1e by sulfonylation due to the presence of a stereogenic center within the
using (E)-styrylsulfonyl chlorides.
tether between the reactive moieties was high (8c, d,
The results of the rhodium-catalyzed CCCC reac- f). The relative configurations of cycloadducts 9 were
tion of substrates 8 are shown in Scheme 3. Gratify- determined by NOE studies; moreover, the crystal
ingly, the cycloaddition of 8a–d and 8e–h occurred structures of 9a, 9c and 9f were determined by X-ray
smoothly to give the g-sultones 9a–d and d-sultones diffraction analysis.[26] In the case of the chiral sub-
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Scheme 3. CCCC reaction of vinylsulfonates 8a–h. Reagents and conditions: a) 3 mol% Rh
perature for 8f).
2ACTHNUGTREN(NUNG oct)4, CH2Cl2, 08C (room tem-
strates (+)-8c and (ꢁ)-8d, the optically active sultones
Synthesis of 16 commenced with the known com-
(ꢁ)-9c and (+)-9d were isolated. Substitution at the pound 10 (Scheme 4).[28] Allylation of 10 gave rise to
vinylsulfonate moiety (R4 ¼H) was tolerated, and the a mixture of C-allylated product 11 and the corre-
olefin geometry in 8g, h was fully retained in the cy- sponding O-allylated isomer. Claisen rearrangement
cloaddition to give the sultones 9g, h as single diaste- of the latter also afforded tricarbonyl compound 11,
reomers. The effect of different rhodium(II) catalysts which was thus isolated in a total yield of 81% from
– rhodium(II) acetate [Rh
noate [Rh2A(oct)4], and rhodium(II) trifluoroacetate and subsequent chemoselective silylation of the pri-
[Rh2A(tfa)4] – on the yield and diastereoselectivity of mary alcohol, oxidation of the remaining diol resulted
2ACHTUNGRTEN(NUNG OAc)4], rhodium(II) octa- 10. After hydride reduction of 11 to furnish a triol
CHTUNGTRENNUNG
CHTUNGTRENNUNG
the reaction was briefly examined. The results were in the desired meso 2,2-disubstituted 1,3-diketone 12.
rather similar for the three catalysts, producing yields Whereas no conversion was noted upon treatment of
varying in the range of ꢀ5–8%. Generally, Rh
(oct)4 12 with bakerꢁs yeast,[29] a Noyori asymmetric transfer
2ACHTUNGTRENNUNG
was found to be the best choice for substrates 8.
hydrogenation catalyzed by [(S,S)-TsDPEN]RuACHTUNGTRENNUNG(p-
The high yield, good diastereoselectivity, and ease cymene)[30] efficiently desymmetrized 12 to yield a
of this CCCC reaction are not trivial, as underscored monoreduction product with high diastereoselectivity
by the finding that the corresponding acrylate of 7c (dr=12:1) as well as enantioselectivity (93% ee).
(acryloyl chloride, Et3N, CH2Cl2, 08C, 85%) only gave While its relative configuration was experimentally
rise to a 6% yield of diastereomeric g-lactone ana- determined by NOE studies, its absolute configura-
logues of 9c (dr=2.6:1), under the conditions used for tion was tentatively assigned as depicted in (ꢁ)-13.
the synthesis of sultone 9c.[27]
Following protection and ozonolysis to afford alde-
Having established the feasibility of the concept by hyde (ꢁ)-14, the remaining steps to vinylsulfonate
demonstrating the first carbene cyclization cycloaddi- (+)-15 were accomplished in high yields similar to the
tion cascade (CCCC) reactions employing vinylsulfo- synthesis of compounds 8.
nates, the next challenge was to apply this expertise
to synthesize more complex sultones, such as the pounds, Rh
tetracyclic sultone 16 (Scheme 5) containing the alyst for the CCCC reaction of (+)-15, giving tetracy-
After experimenting with several dirhodium com-
CTHUNGTRENNUNG
ACHTUNGTRENNUNG
hydro
G
clic sultone (+)-16 in 90% yield as the only diastereo-
mer observed (Scheme 5).
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Scheme 4. Synthesis of vinylsulfonate (+)-15. Reagents and conditions: a) allyl bromide, K2CO3, DMF, microwaves, 608C; b)
DMF, toluene, microwaves, 1808C, 81% from 10; c) LiAlH4, THF, room temperature, 85%; d) TBSCl, cat. DMAP, Et3N,
CH2Cl2, room temperature, 75%; e) Dess–Martin periodinane, CH2Cl2, room temperature, 100%; f) 11 mol% [(S,S)-
TsDPEN]RuACHTUNGTRENNUNG(p-cymene), isopropyl alcohol, room temperature, 81%, 93% ee; g) benzoyl chloride, DMAP, CH2Cl2, room
temperature, 100%; h) O3, CH2Cl2, MeOH, ꢁ788C, then Ph3P, room temperature, 100%; i) N2CHCO2Et, cat. SnCl2, CH2Cl2,
room temperature, 83%; j) TsN3, Et3N, MeCN, 08C, 82%; k) 40% aqueous HF/MeCN (5/95), ꢁ158C, 83%; l)
CH2=CHSO2Cl, (i-Pr)2NEt, CH2Cl2, ꢁ108C, 79%.
13C NMR (125 MHz, CDCl3): d=199.32, 164.79, 91.50,
90.92, 70.55, 62.75, 61.77, 36.25, 32.99, 29.80, 14.03; LR-MS
(ESI): m/z=291.0 [M+H]+, 340.0 [M+CH3OH+NH4]+;
anal. calcd for C11H14O7S: C 45.51, H 4.86, S 11.05; found: C
45.54, H 4.86, S 10.94.
Acknowledgements
Scheme 5. CCCC reaction yields sultone-bridged hydroazu-
lene (+)-16.
Financial support of this work by the DFG (ME 776/15-2),
the DAAD (D/03/314304), DAAD-RGC (G HK026/03),
RGC (HKU 7018/07P), and the AoE Scheme of UGC Hong
Kong (AoE/P-10/01), is gratefully acknowledged.
Further synthetic elaboration of the cycloadducts 9
and (+)-16 is ongoing, and desulfurization is being ex-
plored to provide an access to sulfur-free functional-
ized seven-membered carbocycles.
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