Vol. 9, No.

1

MIDA-protected Boronate Esters

Features include: MIDA as a Protecting Group and Iterative Cross-Coupling Synthesis of Polyene Natural Products Using Polyene MIDA Boronates Formation of Complex Boronic Acids from MIDA Boronates

trans-2-bromovinylboronic acid MIDA ester, a highly versatile and useful surrogate boronic acid building block

Introduction
The Suzuki-Miyaura cross-coupling reaction is one of the most important and highly utilized reactions in organic chemistry, with applications in polymer science as well as in the fine chemicals and pharmaceutical industries. However, some classes of boronic acids are exceptionally unstable and susceptible to decomposition which renders them inefficient in coupling reactions or makes long-term storage difficult. Additionally, performing iterative Suzuki Miyaura cross-couplings under mild conditions for the synthesis of small molecules is limited due to the reactivity of boronic acids and therefore a method to allow for iterative couplings under mild conditions has not been previously developed. The mechanism of transmetalation in Suzuki reactions may involve formation of an “ate” complex via interactions Josephine Nakhla between the base and the vacant p orbital on the sp2 hybridized boron atom. Product Manager Burke and coworkers predicted that a trivalent heteroatomic ligand, such as N-methyliminodiacetic acid (MIDA) (Figure 1) on the boron atom would rehybridize this center to sp3 and thereby attenuate transmetalation under cross-coupling conditions. Release of the reactive, sp2-hybridized boron-species under orthogonal mild conditions would enable this O CH3 O reactivity to be turned back on. In practice, it was N HO OH discovered that the trivalent MIDA is very effective MIDA (N-methyliminodiacetic acid) in this role.1 sp3-Hybridized MIDA boronates are M51008 unreactive towards transmetalation (see Figure 2 for Figure 1 comparison of sp2 and sp3-hybridized boron species) and the ligand can be cleaved under mild conditions H3C N to liberate the corresponding boronic acid. This OH R B O enables the execution of sequential Suzuki-Miyaura B O vs. OH R O O reactions under mild conditions. The MIDA-protected boronate esters are easily handled, indefinitely bench-top stable under air, compatible with chromatography, and unreactive under standard anhydrous cross-coupling conditions, even at temperatures up to 80 °C. However, deprotection is easily achieved at room temperature under mild aqueous basic conditions using either 1M NaOH, or even NaHCO3.
Figure 2
sp2-reactive sp3-unreactive

Vol. 9 No. 1
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Sigma-Aldrich® is committed to providing the most extensive portfolio of high-quality boronic acids, boronate and MIDA esters, and trifluoroborate salts for use in Suzuki coupling, and we continually expand our product listing. This ChemFiles is dedicated to our new product portfolio for MIDA esters. If you are unable to find a coupling reagent for your research, “Please Bother Us” at josephine.nakhla@sial.com, or contact your local Sigma-Aldrich office (see back cover).
Reference: (1) Gillis, E. P.; Burke, M. D. J. Am. Chem. Soc. 2007, 129, 6716.

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Table of Contents
Introduction............................................................................................................................ 2 MIDA as a Protecting Group and Iterative Cross-Coupling................................................. 3 Synthesis of Polyene Natural Products Using Polyene MIDA Boronates............................ 4 Formation of Complex Boronic Acids from MIDA Boronates ............................................. 5 Preparation of trans-(2-bromovinyl) MIDA Boronate and Vinyl MIDA Boronate from the Corresponding Silanes ...................................................... 6 Synthetic Utility of Vinyl MIDA Boronate ............................................................................ 6 MIDA Ligand .......................................................................................................................... 7 Alkyl MIDA Boronates ........................................................................................................... 7 Alkenyl MIDA Boronates ....................................................................................................... 8 Alkynyl MIDA Boronates ....................................................................................................... 8 Aryl MIDA Boronates ............................................................................................................. 8 Heteroaryl MIDA Boronates ................................................................................................ 10

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About Our Cover
The image on the cover represents the three-dimensional structure of trans-2-bromovinylboronic acid MIDA ester. The bromine atom is represented in purple. This B-protected haloboronic acid is representative of many powerful new reagents for iterative cross-coupling.

2

MIDA as a Protecting Group and Iterative Cross-Coupling
To demonstrate the efficacy of MIDA as a protecting group, Burke’s group reacted a 1:1 mixture of the MIDA boronate 698229 and 4-butylphenylboronic acid with 4-bromobenzaldehyde under Buchwald’s anhydrous Suzuki-Miyaura conditions (Scheme 1). The resultant product mixture displayed a 24:1 preference for reaction with the unprotected boronic acid. A control experiment using p-tolyl boronic acid in lieu of 698229 provided a 1:1 mixture of the two products. Additionally, when a control reaction employing the N-methyldiethanolamine adduct instead of the N-methyliminodiacetic acid was performed, no selectivity was observed, presumably due to the increased flexibility of the N-methyldiethanolamine derivative. Various halo-containing MIDA-derivatives were prepared, cross-coupled with boronic acids, and sequentially deprotected under basic conditions to release the unprotected boronic acid, thereby demonstrating the utility towards iterative cross-coupling (Scheme 2). The potential for iterative cross-couplings using the Burke methodology was further demonstrated in their total synthesis of ratanhine (Scheme 3). trans-1-Propen-1-ylboronic acid was coupled with the benzofuranyl MIDA boronate 1, which was deprotected and cross-coupled with the bulky aryl bromide MIDA boronate 2 at elevated temperature. The subsequent intermediate was deprotected and coupled with vinyl bromide 3 to yield the diMOM ether. Cleavage of the two MOM groups resulted in ratanhine, in seven steps in the longest linear sequence. Enabling features of this type of synthesis include the use of only a single, mild reaction to assemble a collection of easily synthesized, readily purified, and highly robust building blocks. Moreover, the short and modular nature of this pathway enables the easy preparation of analogs simply by substituting modified building blocks into the same iterative cross-coupling sequence.1
Reference: (1) Gillis, E. P.; Burke, M. D. J. Am. Chem. Soc. 2007, 129, 6716.

B(OH)2 n-Bu 1 equiv + H3C N O O

CHO CHO Br Pd(OAc)2 JohnPhos K3PO4, THF 65 °C, 6 h H3C

n-Bu + CHO 24:1

MIDA as a Protecting Group

B O O H3C 698229 1 equiv

Scheme 1
H3 C N B O O 701092 PCy2 K3PO4, THF, 65 °C O O H3C N B O O 81% O O

Br

S

p-Tol-B(OH)2 Pd(OAc)2

p-Tol

S

1 M aq. NaOH THF, rt, 10 min

p-Tol

S B(OH)2 88%

Scheme 2
H3C O H 3C

Pd(OAc)2 H 3C B(OH)2 + 1 Cyclohexyl JohnPhos K3PO4, THF 65 °C, 15 h, 80% H3CO O OMOM H3 C H3C N H3CO O OR H3C (i) HCl, MeOH, 65 °C, 1 h Prep HPLC, 41% (unoptimized) RO (i) R = MOM R = H, ratanhine O O B O O

N O O

B O O

1) aq. NaOH, THF 23 °C, 10 min, 93% 2) 2, Pd2(dba)3 Cyclohexyl JohnPhos K2CO3, THF 80 °C, 28 h, 73%

1) aq. NaOH, THF 25 °C, 10 min, 99% 2) 3, Pd2(dba)3 Cyclohexyl JohnPhos K2CO3, THF 65 °C, 20 h, 81%

O O

CH3

Br H3C H3C O Br 1 N Br O O H CO 3 2 CH3 N O O MOMO 3 O O

B O O

B O O OMOM

Scheme 3

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3

Synthesis of Polyene Natural Products Using Polyene MIDA Boronates
Synthesis of Polyene Natural Products
Palladium-catalyzed cross-coupling reactions are ideal methods for the synthesis of polyenes because of the stereospecificity of the reactions and the mildness of the reaction conditions. However, polyenylboronic acids are very unstable and therefore difficult to employ in the synthesis of polyenes via Suzuki reactions. In another exemplary demonstration of the MIDA boronates’ stability and efficiency in iterative cross-coupling, Burke and coworkers utilized a common alkenyl MIDA boronate (703478) to create a series of polyenyl building blocks. The MIDA boronate terminus is inert to Heck, Stille, and Suzuki couplings, yielding butadienyl MIDA boronates (Scheme 4). The alkenyl MIDA boronate 703478 was also applied to the synthesis of the carotenoid all-trans-retinal. Demonstrating the feasibility of polyenyl MIDA boronates in synthesis, boron deprotection of the intermediate 4 proceeded smoothly to generate the boronic acid, which was subsequently coupled with the β-bromo enal to provide all-trans-retinal (Scheme 5). Miyaura borylation (Scheme 6, to provide 6) and Sonogashira and Negishi couplings (to provide 5 and 7, respectively) that yield bis-metalated lynchpin-type reagents were also demonstrated. Synthetic reagent 6 was further elaborated in the polyene natural product synthesis of β-parinaric acid (Scheme 7) and reagent 7 was employed in the preparation of the polyene chain of amphotericin B (Scheme 8).2
Reference: (2) Lee, S. J.; Gray, K. C.; Paek, J. S.; Burke, M.D. J. Am. Chem. Soc. 2008, 130, 466.
CH3 Me Me Me O B O

H 3C TMS Pd(PPh3)4, CuI piperidine, THF, 23 °C 73% TMS

N O O

B O O 5

H3C

N O O

Me Me Me Me

O B O
2

H3C Me Me Me O

N O O

Br

B O O 703478

PdCl2(CH3CN)2 SPhos, KOAc PhMe, 45 °C 71%

B O

B O O 6

Me

Bu3Sn

ZnCl

H3C

Pd(OAc)2, SPhos THF, 0 °C 66%

N O O

Bu3Sn

B O O 7

Scheme 6
H3C N O O B(OH)2 I Cl PdCl2dppf K3PO4, DMSO 23 °C, 54% H3C N O O CH3 Pd(OAc)2, XPhos K3PO4, THF, 45 °C

B O O 6

Cl

B O O

Me

H3C

N O O

1. aq NaOH, THF, 23 °C
7

7

B O O

2. I

CO2H CH3 β-parinaric acid

CO2H

Pd(OAc)2, XPhos aq NaOH, THF, 23 °C 86%

Ph

B(OH)2

H3C

Scheme 7
N O O Bu3Sn 7 H3C N I Cl O Pd2dba3, Ph3As O DMF, 23 °C 72% H 3C N O O N O O H3C N O O

Pd(OAc)2, SPhos PhMe, KF, 23 °C 92% Ph

B O O

B O O

Cl

3

B O O 8

H3C

N O O

Br

B O O 703478

SnBu3 Pd2dba3 P(fur)3 DMF, 45 °C 91%

H3C

N O O (HO)2B Br CH3

B O O

B O O 703478

CH3 CH3

H3CO O Pd(OAc)2, PPh3 Et3N, DMF, 45 °C 90%

Pd(OAc)2, SPhos KF, PhMe, 23 °C 96%

O B O

H3C H3CO O

N O O 1) aq. NaOH THF, 23 °C N O O CH3 CH3
5

H3C TESO H 3C

OAc Me Cl

B O O

Scheme 4
H3C

2) 8, Pd(OAc)2, XPhos Cs2CO3, PhMe, 23 °C 42% H3C

O B O

Pd(OAc)2, XPhos, 1N NaOH THF, 45 °C, 48%

N O O H3C H3C CH3 CH3 N O O

OAc Me CH3

H3C

CH3

CH3 B(OH)2

Br

B O O 703478

TESO H3C

CH3

Pd(OAc)2, SPhos K3PO4, PhMe, 23 °C 78%

B O O 4

CH3

Polyene chain amphotericin B

1. aq NaOH, THF, 23 °C CH3 H 2. O Br Pd(OAc)2, SPhos K3PO4, THF, 23 °C 66%

Scheme 8
CH3 CH3 H O CH3 all-trans-retinal

H3C

CH3

Scheme 5

4

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Formation of Complex Boronic Acids from MIDA Boronates
Another extremely useful feature of the MIDA boronates is their compatibility with a wide range of common synthetic reagents, allowing for the elaboration of functionalized MIDA boronates to create structurally complex boronic acid surrogates. This was recently demonstrated by Burke and coworkers with the transformation of the 4-(hydroxymethyl)phenyl MIDA boronate 698105 by a variety of common oxidants and other reagents to create an array of synthetically useful MIDA boronates (Scheme 9). Even harsh reagents such as triflic acid, and Jones oxidant were well tolerated, and the MIDA boronate was left intact. In several cases, transformations can be easily reversed to yield the original 4-(hydroxymethyl)phenyl MIDA boronate. The 4-formylphenyl MIDA boronate 697494 was further elaborated in various C-C bond-forming reactions. The results show that MIDA

boronates are also compatible with Evans aldol, Horner-WadsworthEmmons olefination, and Takai olefination protocols. Reductive amination is also well-tolerated (Scheme 10). The impact of the exceptional compatibility of the MIDA boronate was exhibited in the total synthesis of (+)-crocacin C starting from an acrolein MIDA boronate (Scheme 11). The MIDA boronate tolerated a Paterson aldol and diastereoselective reduction protocol to yield the diol MIDA boronate, which was purified by silica gel chromatography. The purified MIDA boronate was permethylated with Meerwein’s salt, deprotected with CAN, oxidized with Dess-Martin periodinane and subjected to Takai olefination to yield the stable, crystalline, complex MIDA boronate 9. Stille coupling of 9 with known building block 10, followed by in situ boronic acid release and cross-coupling with bromobenzene provided (+)-crocacin C.3
Reference: (3) Gillis, E. P.; Burke, M. D. J. Am. Chem. Soc. 2008, 130, 14084.

Formation of Complex Boronic Acids

H3C

N O O

PMBO

B O O

PMBOC(NH)CCl3 TfOH, THF, 0→23 °C 5 h, 64% DDQ, DCM 23 °C, 1.5 h, 79%

H3C CrO3, H2SO4, Acetone 23 °C, 30 min, 90% HO O

N O O

B O O

H3C

N O O

H3C TBSCl, Imid, THF 23 °C, 9 h, 98% HF•py, THF 23 °C, 1 h, 88%

N O O

TBSO

B O O

B O O OH 698105

H3C (COCl)2, DMSO

N O O

H3 C

N O O PPh3, I2, Imid, THF 23 °C, 1 h, 88%

B O O I

CH2Cl2, Et3N, 88% NaBH4, THF:EtOH 0 °C, 2 h, 65%

H O

B O O 697494

Scheme 9
Bn Et O N On-Bu2BOTf, Et3N, DCM O -78→ 0 °C, 2 h H2O2, MeOH pH 6.0 buffer, 79% Bn O O N O OH H3C O H3C EtO N O O O P(OEt)2 EtO O H3C CrCl2, CHI3 THF:dioxane 23 °C, 1 h, 88% I N O O I OMe OMe 9 H3C morpholine, NaBH(OAc)3 DCE, 23 °C, 8 h, 76% H 3C CH3 CH3 N O O N O O CH3 CH3 Sn(OTf) , Et N 2 3 O DCM, -78 °C 12 h, 70% PMBO CH3 CH3 OH OH

H3C

N O O H O

H3C

1) N O O PMBO

H3C

N O O

CH3

B O O

B O O

2) Me4N(OAc)3BH, AcOH MeCN, -30 °C, 6 h, 71% H3C CH3 CH3 OH OMe OMe H2N O N

B O O

1) Me3OBF4, proton sponge DCM, 23 °C, 2.5 h, 82% 2) CAN, MeCN:H2O 23 °C, 15 min, 77%

B O O

B O O

O O

1) DMP, DCM 23 °C, 15 min, 97% 2) CHI3, CrCl2 THF:dioxane 23 °C, 1 h, 74%

NaH, DMF 23 °C, 30 min, 71%

H O

B O O

SnBu3 CH3 10

697494

B O O

B O O

Pd(PPh3)4, CsF, CuI DMF, 23 °C, 5 h, 62% H3C N PhBr, Pd(OAc)2 SPhos O O K3PO4, THF:H2O 60 °C, 24 h

N O O

CH3 CH3 H2N O CH3 OMe OMe

O N

B O O

B O O

Scheme 10
H2N O CH3

CH3 CH3 OMe OMe (+)-crocacin C

Scheme 11

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5

Preparation of trans-(2bromovinyl) MIDA Boronate

Preparation of trans-(2-bromovinyl) MIDA Boronate and Vinyl MIDA Boronate from the Corresponding Silanes
Due to the instability of some boronic acids, the Burke group has developed very practical syntheses of some of the more challenging MIDA boronates. For instance, while trans-(2-bromovinyl) MIDA boronate (703478) could be prepared via bromoboration of acetylene and reaction with MIDA in the presence of base, a more convenient procedure was subsequently developed. The synthesis of trans-(2-bromovinyl) MIDA boronate is achieved via transmetalation of 1-bromo-2-trimethylsilylethylene with BBr3, followed by trapping with MIDA2-Na2+ to form the MIDA boronate (Scheme 12-(1)). This procedure also gave rise to the very useful building block, vinyl MIDA boronate (704415) (Scheme 12-(2)). Of note, the corresponding boronic acid is very unstable.4

H3C TMS (E:Z 9:1) BBr3 CH2Cl2 0 °C, 2 h; MIDA2-Na2+ CH3CN 0 °C, 1 h

N O (1) O

Br

Br

B O O (E only) 703478 61% H3C

TMS

BBr3 CH2Cl2 0 → 23°C, 2.5 h; MIDA2-Na2+ CH3CN 0 → 23°C, 1 h

N O O (2)

B O O 704415 86%

Scheme 12

Synthetic Utility of Vinyl MIDA Boronate
The utility of vinyl MIDA boronate was demonstrated via cyclopropanation and epoxidation to the corresponding MIDA cyclopropane and oxirane, respectively. These procedures (Scheme 13) provided air and chromatography-stable solids in both cases, with the oxirane being the first known synthesis of an unsubstituted oxiranylborane (confirmed by X-ray analysis of the oxiranylborane). Vinyl MIDA boronate was also successfully subjected to Heck and oxidative Heck reactions as well as to olefin metathesis (Scheme 14) to provide the desired alkenyl MIDA boronates. The cross metathesis of vinyl MIDA boronate with various olefins represents a potent strategy for the highly stereoselective construction of substituted vinyl boranes. This method proved successful in the preparation of a variety of disubstituted olefins (Scheme 15) with excellent yields (81-98%) and E:Z selectivities (>20:1). This procedure represents a significant advance relative to the cross metathesis with alkenyl pinacol, which can be limited by instability of the alkenyl boronic ester substrates, the stereoselectivity of the transformation, and/or the ease of purification of the resulting products.4
Reference: (4) Uno, B. E.; Gillis, E. P.; Burke, M. D. Tetrahedron 2008, In Press.

Br Me O Pd(PPh3)4, Ag3PO4 THF, 100 °C, 24 h, 64%

H3C

N O O

Me O

B O O

H3C

H3C N O O O • S Ph Pd(OAc)2 PhB(OH)2 BQ, Dioxane, 45 °C, 48 h, 68% O Ph S

N O O

B O O 703478

B O O 699292

H3C CH3 Grubbs II CH2Cl2, 40 °C 12 h, 80% CH3

N O O

B O O

Scheme 14
H3C

N H3C N O O

H3C Pd(OAc)2/CH2N2 Et2O, 0 → 23 °C 1 h, 93% H 3C N

R N O O Entry Cross partner 1.5-2.5 eq

O B O O O 1 equiv Grubbs II CH2Cl2 40 °C, 12 h Cross product H3C N O O R

B O O E:Z>20:1

B O O 697311

Isolated yield (%)

O B O O O 703478 mCPBA CH2Cl2, 0 → 23 °C 18 h, 74% O

1 H3C N O O 2

i-Pr3Si

i-Pr3Si H3C

B O O N

85

B O O

AcO

OAc

AcO H3C

B O O N

O O

84

Scheme 13
3

B O O 703710 H3C HO N

O O

96

4

HO Me ortho meta para Br Me H3C N

B O O

O O

94

5

Br

B O O

O O

ortho 81 meta 91 para 89

Scheme 15

6

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MIDA Ligand
Methyliminodiacetic acid, 99%
O CH3 O [4408-64-4] N Beil. 4,367 HO OH C5H9NO4 FW 147.13 mp................................................................................... 220 °C (dec.)

n-Butylboronic acid MIDA ester
C9H16BNO4 FW 213.04
701580-1G 701580-5G
H3C H3C

8
N O O

B O O

1g

MIDA Ligand

5g 8
H3C N O O

Cyclopentylboronic acid MIDA ester, 97%
C10H16BNO4 FW 225.05
699144-1G

M51008-5G M51008-25G

5g 25 g

Alkyl MIDA Boronates
Allylboronic acid MIDA ester
2-Allyl-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione C8H12BNO4 FW 197.00
698709-1G
H3C

B O O

1g 8
H3C N O O

8
N O O

Cyclopropylboronic acid MIDA ester, 97%
Cyclopropylboronic acid methyliminodiacetic acid anhydride C8H12BNO4 FW 197.00
697311-1G 697311-5G

H2C

B O O

B O O

1g 8
H3C N O O

1g 5g 8
H3C N O O

Benzylboronic acid MIDA ester, 95%
C12H14BNO4 FW 247.05
701114-1G 701114-5G

Methylboronic acid MIDA ester, 97%
C6H10BNO4 FW 170.96
700657-1G 700657-5G

B O O

1g 5g

H3C B O O

1g 5g

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7

Alkenyl MIDA Boronates
trans-2-Bromovinylboronic acid MIDA ester
BB1 C7H9BBrNO4 FW 261.87
703478-500MG 703478-1G
H3C

Alkynyl MIDA Boronates
8
N O O

Ethynylboronic acid MIDA ester
Acetyleneboronic acid MIDA ester; Ethyneboronic acid MIDA ester; Acetynylboronic acid MIDA ester C7H8BNO4 FW 180.95
700231-1G
HC B

8
H3C N O O

Alkenyl MIDA Boronates

Br

B O O

O O

500 mg 1g 8
N O O

1g

trans-(2-Cyclohexylvinyl)boronic acid MIDA ester, 95%
C13H20BNO4 FW 265.11
H3C

Aryl MIDA Boronates
3-Benzyloxyphenylboronic acid MIDA ester, 96%
C18H18BNO5 FW 339.15
H3C O

8
N O O

B O O

703710-1G

1g 8
H3C N O O

B O O

trans-2-Phenylvinylboronic acid MIDA ester, 95%
C13H14BNO4 FW 259.07

699861-1G

1g 8
H3C N O O

B O O

2-Bromophenylboronic acid MIDA ester, 95%
2-(2-Bromophenyl)-6-methyl-1,3,6,2-dioxazaboracane4,8-dione C11H11BBrNO4 FW 311.92
698040-1G 698040-5G

699292-1G

1g 8
H3C H3C N O O

B O O Br

cis-1-Propenylboronic acid MIDA ester
cis-1-Propene-1-boronic acid MIDA ester; cis-6-Methyl2-(1-propenyl)-1,3,6,2-dioxazaborocane-4,8-dione C8H12BNO4 FW 197.00
698199-1G

1g 5g 8
H3C N O O

B O O

3-Bromophenylboronic acid MIDA ester, 96%
2-(3-Bromophenyl)-6-methyl-1,3,6,2-dioxazaborocane4,8-dione C11H11BBrNO4 FW 311.92
Br

1g 8
H3C N O O

trans-1-Propenylboronic acid MIDA ester
C8H12BNO4 FW 197.00
H3C

B O O

B O O

698113-1G 698113-5G

1g 5g

701831-1G

1g

New Palladium Catalysts for Cross-Coupling from Sigma-Aldrich®

Cross-coupling has been a cornerstone set of reactions for the formation of carbon–carbon bonds. For the past twenty years, numerous research groups have developed new metal complexes and ligands, expanding the scope of these transformations to give access to more complex molecules. Among these important reactions, several stand out, such as Suzuki, Negishi, Heck, Kumada, Stille, Sonogashira and Buchwald Hartwig amination reactions. Furthermore, scientists have developed new complexes, usually palladium based, that are able to catalyze the aforementioned reactions, with high yields and low catalyst loadings. Sigma-Aldrich is happy to offer new palladium catalysts for cross-coupling reactions.

P Fe P Pd

Cl Cl Fe

P Pd P

P Cl Cl Fe P Pd

Cl Cl

P Fe P Pd

Cl Cl

PPh3 Ph3P Pd PPh3 PPh3

701602

702005

701998

697230

High Purity 99.9+% 697265

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8

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4-Bromophenylboronic acid MIDA ester, 97%
2-(4-Bromophenyl)-6-methyl-1,3,6,2-dioxazaborocane4,8-dione C11H11BBrNO4 FW 311.92
698083-1G 698083-5G
H3C

8
N O O

4-Formylphenylboronic acid MIDA ester, 96%
4-Formylphenylboronic acid methyliminoacetic acid anhydride C12H12BNO5 FW 261.04
697494-1G
H3C

8
N O O

B O O Br

H O

B O O

Aryl MIDA Boronates

1g 5g 8
H3C O HO N O O

1g 8
H3C N O O

3-Carboxyphenylboronic acid MIDA ester, 96%
3-(6-Methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl) benzoic acid C12H12BNO6 FW 277.04
698091-1G

4-(Hydroxymethyl)phenylboronic acid MIDA ester
2-(4-(Hydroxymethyl)phenyl)-6-methyl-1,3,6,2dioxazaborocane-4,8-dione C12H14BNO5 FW 263.05
698105-1G

B O O

HO

B O O

1g 8
H3C N O O

1g 8
H3C N O O

3-Cyanophenylboronic acid MIDA ester, 97%
3-(6-Methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl) benzonitrile C12H11BN2O4 FW 258.04
698024-1G 698024-5G

3-Hydroxyphenylboronic acid MIDA ester, 97%
2-(3-Hydroxyphenyl)-6-methyl-1,3,6,2-dioxazaborocane4,8-dione C11H12BNO5 FW 249.03
698008-5G

B O O CN

B O O OH

1g 5g 8
H3C N O O

5g 8
H3C N O O

3-Iodophenylboronic acid MIDA ester, 97%
2-(3-Iodophenyl)-6-methyl-1,3,6,2-dioxazaborocane4,8-dione C11H11BINO4 FW 358.92
I

4-Cyanophenylboronic acid MIDA ester, 97%
4-(6-Methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl) benzonitrile C12H11BN2O4 FW 258.04
697990-1G 697990-5G

B O O

B O O N C

1g 5g 8
H3C Br N O O

698156-1G

1g 8
H3C N O O

4-Iodophenylboronic acid MIDA ester, 97%
2-(4-Iodophenyl)-6-methyl-1,3,6,2-dioxazaborocane4,8-dione C11H11BINO4 FW 358.92
698121-1G 698121-5G

2,6-Dibromophenylboronic acid MIDA ester
C11H10BBr2NO4 FW 390.82

B O O I

B O O Br

1g 5g 8
N O O

703044-500MG 703044-1G

500 mg 1g 8
H3C N O O

3-Methoxycarbonylphenylboronic acid MIDA ester, 97%
Methyl 3-(6-methyl-4,8-dioxo-1,3,6,2dioxazaborocan-2-yl) benzoate C13H14BNO6 FW 291.06
698164-1G 698164-5G
H3C O H3CO

4-Fluorophenylboronic acid MIDA ester, 97%
2-(4-Fluorophenyl)-6-methyl-1,3,6,2-dioxazaborocane4,8-dione C11H11BFNO4 FW 251.02
701548-5G

B O O

B O O F

1g 5g 8
H3C N O O

5g 8
H3C N O O

2-Formylphenylboronic acid MIDA ester, 97%
2-(6-Methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl) benzaldehyde C12H12BNO5 FW 261.04
698210-1G 698210-5G

2-Methoxyphenylboronic acid MIDA ester, 97%
2-(2-Methoxyphenyl)-6-methyl-1,3,6,2-dioxazaborocane4,8-dione C12H14BNO5 FW 263.05
698075-1G

B O O H O

B O O OCH3

1g 8
H3C N O O

1g 5g 8
H3C O H N O O

3-Methoxyphenylboronic acid MIDA ester, 97%
C12H14BNO5 FW 263.05

3-Formylphenylboronic acid MIDA ester, 97%
3-(6-Methyl-4,8-dioxo-1,3,6,2-dioxazaborocan-2-yl) benzaldehyde C12H12BNO5 FW 261.04
700932-1G 700932-5G

B O O OCH3

B O O

699160-1G 1g 5g 699160-5G

1g 5g 8
H3C N O O

4-Methoxyphenylboronic acid MIDA ester, 97%
2-(4-Methoxyphenyl)-6-methyl-1,3,6,2dioxazaborocane-4,8-dione C12H14BNO5 FW 263.05
700924-1G 700924-5G

B O O H3CO

1g 5g

Ready to scale up? For competitive quotes on larger quantities or custom synthesis, contact your local Sigma-Aldrich office, or visit safcglobal.com.

9

1-Naphthylboronic acid MIDA ester, 95%
Naphthalene-1-boronic acid MIDA ester C15H14BNO4 FW 283.09
H3C N

8
O O B O O

6-Bromo-3-pyridinylboronic acid MIDA ester, 97%
2-Bromopyridine-5-boronic acid MIDA ester; 2-(6-Bromo-3-pyridinyl)-6-methyl-1,3,6,2dioxazaborocane-4,8-dione; 6-Bromopyridine3-boronic acid MIDA ester C10H10BBrN2O4 FW 312.91
702269-1G
H3C

8
N O O

B O O Br N

Aryl MIDA Boronates

699136-1G

1g 8
H3C N O O

2-Naphthylboronic acid MIDA ester, 95%
C15H14BNO4 FW 283.09

1g 8
H3C N B O O O

5-Bromo-2-thiophenylboronic acid MIDA ester, 95%
5-Bromothiophene-2-boronic acid MIDA ester; 2-(5-Bromothiophen-2-yl)-6-methyl-1,3,6,2dioxazaborocane-4,8-dione C9H9BBrNO4S FW 317.95
701092-1G
Br S

B O O

O

699853-1G

1g 8
H3C N O O

3-Nitrophenylboronic acid MIDA ester, 97%
6-Methyl-2-(3-nitrophenyl)-1,3,6,2-dioxazaborocane4,8-dione C11H11BN2O6 FW 278.03
698148-1G 698148-5G

1g 8

6-Chloro-3-pyridinylboronic acid MIDA ester, 97%

B O O NO2

1g 5g 8
H3C N O O

Phenylboronic acid MIDA ester, 95%
6-Methyl-2-phenyl-1,3,6,2-dioxazaborocane-4,8-dione C11H12BNO4 FW 233.03
698032-1G 698032-5G

H3C 6-Chloro-3-pyridineboronic acid MIDA ester; N 2-(6-Chloro-3-pyridinyl)-6-methyl-1,3,6,2O B O dioxazaborocane-4,8-dione; 2-Chloropyridine-5O O boronic acid MIDA ester Cl N C10H10BClN2O4 FW 268.46 mp................................................................................. 222 to 226 °C

700908-1G

1g 8
H3C N B O O O

B O O

2-Furanylboronic acid MIDA ester, 97%
2-Furanboronic acid MIDA ester; 2-(Furan-2-yl)-6-methyl1,3,6,2-dioxazaborocane-4,8-dione C9H10BNO5 FW 222.99
701017-1G
O

1g 5g 8
H3C N O O

O

4-Tolylboronic acid MIDA ester, 97%
6-Methyl-2-p-tolyl-1,3,6,2-dioxazaborocane-4,8-dione C12H14BNO4 FW 247.05
H3C

1g 8
H3C N O O

2-Methoxy-3-pyridinylboronic acid MIDA ester, 97%
2-Methoxy-3-pyridineboronic acid MIDA ester; 2-(2-Methoxypyridin-3-yl)-6-methyl-1,3,6,2dioxazaborocane-4,8-dione C11H13BN2O5 FW 264.04
701084-1G

B O O

B O O N OCH3

698229-5G

5g 8
H3C N O O

4-Vinylphenylboronic acid MIDA ester, 97%
6-Methyl-2-(4-vinylphenyl)-1,3,6,2dioxazaborocane-4,8-dione C13H14BNO4 FW 259.07
701890-500MG 701890-1G

1g 8
H3C N O O

2-Methoxy-5-pyridinylboronic acid MIDA ester, 97%
2-Methoxy-5-pyridineboronic acid MIDA ester C11H13BN2O5 FW 264.04
H3CO N

H2C

B O O

500 mg 1g

B O O

699845-1G

1g 8
H3C N O N O O S O B O O

Heteroaryl MIDA Boronates
2-Benzofuranylboronic acid MIDA ester, 97%
2-Benzofuranboronic acid MIDA ester; 2-(Benzofuran2-yl)-6-methyl-1,3,6,2-dioxazaborocane-4,8-dione C13H12BNO5 FW 273.05
701106-1G 8
H3C N O B O O O O

1-(Phenylsulfonyl)-2-indolylboronic acid MIDA ester, 96%
1-(Phenylsulfonyl)indole-2-boronic acid MIDA ester; 1-(Phenylsulfonyl)indole-2-boronic acid; Methyliminodiacetic acid anhydride C19H17BN2O6S FW 412.22
697443-1G

1g 8
H3C Br N N O O

5-Bromo-3-pyridinylboronic acid MIDA ester, 95%
5-Bromopyridine-3-boronic acid MIDA ester C10H10BBrN2O4 FW 312.91
703370-1G 703370-5G

1g 8
O O H3C N B O O

4-Pyridinylboronic acid MIDA ester, 95%
4-Pyridineboronic acid MIDA ester C10H11BN2O4 FW 234.02

B O O

1g 5g 699179-1G
N

1g

10

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