Turning Halohydrocarbons into “Transferable Carbon Fragments”: Key Rules and Application Navigation for Grignard Reagents RMgX (Tables 1–4)

1.Why are we always building C–C bonds—yet so often stuck on “control and scale-up”?

In the synthesis of drug leads, fine chemicals, flavors & fragrances, and functional-material monomers, one task keeps recurring: attaching one carbon fragment to another (forming a C–C bond) and obtaining functional groups that enable further derivatization. Among these, alcohols and carboxylic acids are two of the most frequent “end points”.

The real difficulty is often not “whether a reaction exists”, but “whether it can be made stable, predictable, and scalable”:

1. Many common carbon sources (e.g., halohydrocarbons R–X) are not sufficiently “transferable” on their own, making it hard to deliver R efficiently to electrophilic sites such as carbonyls to form a new bond.

2. Once highly reactive reagents are introduced, practical issues quickly arise—side reactions, poor functional-group compatibility, exothermicity, and safety windows—often becoming even more sensitive upon scale-up.

The key value of Grignard reagents is that they convert common halohydrocarbons R–X into transferable carbon fragments RMgX, and enable C–C bond formation with a relatively clear set of rules—thereby efficiently accessing common structural units such as alcohols and carboxylic acids.

2.Basic concept: What is a Grignard reagent?

According to the IUPAC Gold Book, a Grignard reagent is an organomagnesium halide with the general formula RMgX. Its defining feature is the presence of a carbon–magnesium (C–Mg) bond. In ether solvents (e.g., diethyl ether, THF), it commonly exists as solvent-coordinated and/or aggregated species, and can participate in solution equilibria with species such as R₂Mg and MgX₂ (often referred to as the “Schlenk equilibrium”: a redistribution equilibrium in which organic groups and halides are reallocated on magnesium).

 

What do R and X represent in RMgX?

1. R: an organic group (organyl), commonly alkyl/aryl/alkenyl, typically derived from the corresponding R–X precursor.

2. X: a halide, most commonly Cl / Br / I (corresponding to Grignard reagents prepared from organochlorides/organobromides/organoiodides).

 

Victor Grignard shared the 1912 Nobel Prize in Chemistry with Paul Sabatier for the discovery of the “Grignard reagent/Grignard reaction”. The reagent is named after the French chemist Victor Grignard; he was the first to systematically study and promote the use of organomagnesium halides in organic synthesis, and the reagent has since been known by his surname (Grignard reagent).

3.The dual reactivity conferred by the C–Mg bond: both nucleophilic and strongly basic

Reactivity	Key reason (structural basis)	Typical manifestation	Practical handling implications
Strong nucleophilicity (for C–C bond formation)	The C–Mg bond is highly polarized; the carbon end shows “carbanion-like” character	Preferential attack on electrophilic carbon centers, typically the carbonyl carbon (aldehydes/ketones/esters, etc.)	Choose an appropriate electrophile; control temperature and addition rate to minimize side reactions
Strong basicity (readily quenched by proton sources)	High electron density at the carbon end makes acid–base reactions facile	In the presence of water, alcohols, acids, ammonium salts, and other “active-hydrogen” species, it is quenched first (acid–base quench before any addition chemistry)	Strictly anhydrous conditions and an inert atmosphere (N₂/Ar); avoid substrates/solvents/additives containing readily protonatable hydrogens
Common scale-up risks: exothermicity and unstable initiation	Heat may be released rapidly during formation/reaction; initiation is influenced by surface effects and mass transfer	Both preparation and addition often involve noticeable heat release; scale-up more readily shows “delayed initiation/sudden onset”, temperature excursions, and side reactions	On scale-up, focus on initiation, heat release, dosing rhythm, and cooling capacity; if needed, use portionwise charging/dropwise addition and on-line temperature control

4.How to prepare: turning halohydrocarbons into RMgX

1. Typical preparation reaction:

R–X + Mg (ether solvents such as diethyl ether/THF) → RMgX

2. Practical Q&A:

a) Why must the conditions be “anhydrous + inert atmosphere”?

The C–Mg bond in RMgX is highly reactive; once it encounters water/acid/oxygen, it is consumed or deactivated. Therefore, both preparation and use are typically carried out as dry as possible, under an inert atmosphere such as N₂/Ar.

b) Why are some fast and others slow? (common empirical order)

From practical experience regarding formation/initiation: R–I is usually the easiest to form a Grignard reagent, R–Br next, while R–Cl often requires more stringent conditions (especially aryl chlorides). In addition, many aryl chlorides are indeed slower under conventional conditions and may be difficult to initiate, whereas aryl bromides/iodides are typically more feasible (details also depend on substrate substitution, solvent, and the surface state of Mg).

5.The three most common uses: how Grignard reagents turn “halohydrocarbons” into usable carbon fragments

Main use line	Typical reaction partner	What you obtain after workup (acid quench / hydrolysis)	When to use it	Key reminders
A. Carbonyl addition (build C–C bonds → alcohols)	Formaldehyde / aldehydes / ketones	Formaldehyde → primary alcohol; aldehyde → secondary alcohol; ketone → tertiary alcohol	Rapid scaffold extension; homolog / SAR comparisons; attaching a fragment onto a carbonyl to generate an alcohol handle for further derivatization	Addition first, then acid workup; the system is highly sensitive to water/acid—any “active hydrogen” in the substrate will preferentially quench RMgX
B. CO₂ capture: one-carbon source → carboxylic acids	CO₂ (dry ice / CO₂)	RCO₂H (carboxylic acid)	Quickly accessing acid intermediates from halides (also commonly used with isotopically labeled CO₂ strategies)	Requires acid workup to reveal the acid; still demands anhydrous conditions and avoidance of proton sources that quench the reagent first
C. The classic significance (upgrading halides into “controlled carbon-fragment donors”)	RMgX is first prepared from R–X	RMgX participates as a “transferable R⁻ equivalent” in downstream reactions	Many syntheses bottleneck at “how to introduce a carbon fragment stably and predictably”; Grignard reagents remain high-frequency tools because the starting materials are accessible and the reactions are direct	Real systems are multi-species solutions with distributions of coordinated/aggregated forms

Note for Use A: 

For acyl chlorides/esters, Grignard reagents typically undergo double addition, and after acidic workup the major products are often tertiary alcohols. If the target is a ketone, Weinreb amides or organocopper/organ zinc systems are commonly used to achieve single acylation.

6.How to classify Grignard reagents: R determines “what carbon fragment is delivered”, X determines “how easy it is to make”

6.1 By the R group (what carbon fragment is being transferred)

R type	Typically “introduces what structure”	Typical use tendency
Alkyl	Saturated carbon chains / side chains	Scaffold extension; homolog/side-chain optimization
Aryl	Aromatic ring fragments	Aromatic fragment installation; substitution-pattern comparisons
Heteroaryl	Aromatic rings containing N/O/S	Common in fragments/leads, but requires closer attention to stability and side-reaction risks
Vinyl	C=C fragments (non-allylic)	Introduction of unsaturation as a handle for downstream functionalization
Allyl / Benzyl	“Activated” π-adjacent carbon fragments	Rapid allyl/benzyl installation; selectivity/side reactions are more system-dependent
Alkynyl	C≡C fragments	Installing alkynes (for click chemistry/additions/hydrogenation, etc.)

6.2 By X (Cl/Br/I) + substrate type (controls “whether it forms / how fast it initiates”)

Dimension	Empirical trend
Halide X	Typically I > Br > Cl (further right = easier/faster initiation); Br is the most common compromise; Cl is often harder and more condition-sensitive (but not necessarily impossible)
Substrate type	In many cases, alkyl/aryl/vinyl iodides or bromides are easier to prepare; many aryl chlorides are slower or harder to initiate under conventional conditions
Additional note	Fluorides (R–F) are generally not used to prepare Grignard reagents (the C–F bond is too strong and F is a poor leaving group)

7.Boundaries and risks: when are Grignard reagents not suitable?

The “strong base + strong nucleophile” nature of Grignard reagents defines clear practical boundaries:

1. They are quenched first by proton sources.

If the substrate or reaction medium contains –OH, –COOH, or readily proton-donating N–H / ammonium salts (e.g., ammonium salts or sufficiently acidic N–H sites), an acid–base reaction often happens first, consuming RMgX and preventing the main reaction from proceeding. (Reason note: RMgX is protonated to give RH (a hydrocarbon) and magnesium salts such as carboxylates/alkoxides; these salts are typically not reactive for subsequent nucleophilic C–C bond-forming additions, effectively “shutting down” the desired pathway.)

2. Selectivity can be poor toward certain strongly electrophilic functional groups.

With highly electrophilic sites (e.g., acid derivatives), Grignard reagents may over-add or trigger side reactions. You may need to evaluate switching to milder organometallics, applying protecting groups, or redesigning the synthetic route.

3. Scale-up process risks must be managed up front.

Preparation and reactions are often exothermic, and initiation can be uncertain (induction periods / sudden onset). Charging and stirring can also create localized heat accumulation. Scale-up typically requires more systematic temperature control, dosing strategy, and on-line monitoring / risk controls.

8.Grignard reagent product navigation table: locate products by research task (linked to Tables 1–4)

Typical research task / experimental need	Which table to consult	Why start here (selection logic)
Run the most common “Grignard addition” to build carbon scaffolds: aldehydes/ketones → alcohols (methylation, ethylation, butylation, etc.)	Table 1	First define the alkyl type you want to install (Me/Et/Bu/i-Bu/sec-Bu/t-Bu/c-Hex), then choose within that class by solvent (THF/Et₂O/2-MeTHF/mixed ethers) and concentration/spec to match screening vs scale-up.
Need “methyl installation” with attention to reactivity and process window: how to choose MeMgCl vs MeMgBr vs MeMgI	Table 1	All are “methylation”, but halide and solvent affect reactivity, heat release, and side-reaction windows; Table 1 consolidates common MeMgCl/MeMgBr/MeMgI formulations for direct comparison.
The system is highly solvent-sensitive: want to compare THF / Et₂O / 2-MeTHF / higher-boiling ethers / THF–toluene mixtures	Table 1	This is fundamentally a trade-off among solubility, reactivity, and scale-up operability; Table 1 provides multiple solvent versions for the same alkyls (especially Me, Et, t-Bu, c-Hex) for quick selection.
Build an “allylic alcohol / alkene handle”: allylation (AllylMgBr) or vinylation (vinyl Grignard)	Table 2	If the goal is installing a C=C handle for downstream oxidation/cyclization/coupling, start with the unsaturated Grignard collection.
Build “propargyl alcohol / alkynoic acid / alkynyl side chains”: alkynyl installation (ethynyl / 1-propynyl)	Table 2	Alkynyl Grignards are often more sensitive and may require stricter drying and temperature control; Table 2 concentrates alkynyl entries for rapid selection across alkynyl addition / epoxide opening / CO₂ carboxylation routes.
Need aryl installation / aryl alcohol construction / aryl acids (via CO₂ carboxylation): PhMgX, p-tolylMgBr	Table 3	Functional-group tolerance and downstream utility (addition, carboxylation, Kumada coupling) drive selection for aryl/benzyl Grignards; Table 3 compares Ph / p-tolyl / Bn series side-by-side for structure and concentration-based choices.
Need benzyl installation (BnMgX): benzylation or SAR controls as a hydrophobic anchoring fragment	Table 3	Benzyl Grignards are widely used for rapid benzyl side-chain installation (carbonyl addition and electrophile trapping); Table 3 groups BnMgCl/BnMgBr across concentrations for dosing accuracy and scale-up needs.
Do Kumada coupling (Ni/Pd) to build C–C bonds: alkyl/vinyl/aryl organomagnesium coupling partners	Table 1 / Table 2 / Table 3	First route by organomagnesium type: alkyl → Table 1; vinyl/allyl/alkynyl → Table 2; aryl/benzyl → Table 3. Coupling outcomes depend strongly on substrate class and stability—pick the right class first, then refine the spec.
Need halogen–magnesium exchange / controlled metalation to generate aryl/heteroaryl magnesium intermediates (then trap an electrophile)	Table 4	This is a different task from “standard additions”: it depends more on exchange rate, controllability, and substrate compatibility. Table 4 concentrates i-PrMgCl and i-PrMgCl·LiCl (Turbo), the primary entry points for this workflow.
Substrates are sensitive; want faster and more controllable exchange/metalation: prioritize Turbo Grignard (i-PrMgCl·LiCl)	Table 4	i-PrMgCl·LiCl is commonly used for faster, more controllable halogen–Mg exchange/metalation; Table 4 centralizes these tool reagents for sensitive heteroarenes, low-temperature windows, and rapid trapping.
Need a “transformable one-carbon / alkene-building module”: TMSCH₂MgCl (silylmethyl Grignard)	Table 4	This is a “functionalized Grignard” rather than a simple Me/Et reagent: often used for carbonyl addition to form β-silyl alcohols, followed by elimination/desilylation to build alkenes. Table 4 is dedicated to compiling such specialized entries.

Table 1 | Alkyl Grignard Reagents (Me / Et / Bu / i-Bu / sec-Bu / t-Bu / cyclohexyl, etc.)

Category	CAS No.	Aladdin Cat. No.	Name	Specification / Purity	Product features & applications
Alkyl Grignard reagents | Methyl (Me)	676-58-4	M119433	Methylmagnesium chloride solution	3.0 M in THF	MeMgCl: A high-frequency “methylation” nucleophile for aldehyde/ketone addition, acyl halide/ester transformations (equivalents must be controlled), epoxide ring-opening, etc. 3.0 M is suited to scale-up and reduced solvent volume; note strong exothermicity and control temperature via dropwise addition.
Alkyl Grignard reagents | Methyl (Me)	75-16-1	M130052	Methylmagnesium bromide	1.0 M solution in THF	MeMgBr (THF): Commonly used for standard methyl installation and as a methodological benchmark; strong THF coordination gives higher reactivity, suitable for low-temperature fast additions and substrates requiring stronger driving force.
Alkyl Grignard reagents | Methyl (Me)	75-16-1	M130050	Methylmagnesium bromide	3.0 M solution in diethyl ether	MeMgBr (Et₂O, high concentration): Suitable for scale-up charging and space efficiency; used for methylation additions/ring-opening/carboxylation, etc. Titration before use is recommended to ensure accurate effective concentration.
Alkyl Grignard reagents | Methyl (Me)	75-16-1	M130051	Methylmagnesium bromide	3.0 M solution in 2-methyl-THF	MeMgBr (2-MeTHF): A more process-friendly solvent system for methyl installation and scale-up; often chosen as an alternative when seeking a better process window or lower solvent usage.
Alkyl Grignard reagents | Methyl (Me)	75-16-1	M433580	Methylmagnesium bromide solution	1.0 M in dibutyl ether	MeMgBr (DBE): Higher-boiling ether system, suitable when a higher temperature window is needed or to reduce solvent volatility effects; more convenient for process handling in scale-up methylation/addition steps (still manage peroxide risk and keep strictly dry).
Alkyl Grignard reagents | Methyl (Me)	75-16-1	M433581	Methylmagnesium bromide solution	1.4 M in THF:toluene (1:3)	THF/toluene system: Balances solubility and reactivity; useful when substrates have limited solubility in neat THF or when reducing overly strong coordination effects is desired in addition/metalation steps.
Alkyl Grignard reagents | Methyl (Me) / higher reactivity	917-64-6	M140783	Methylmagnesium iodide	3.0 M in diethyl ether	MeMgI is typically more reactive: Used when higher reactivity is required for methylation addition/trapping steps (can be faster than Cl/Br systems for some substrates). Higher cost and higher activity demand tighter control of temperature and equivalents to avoid side reactions.
Alkyl Grignard reagents | Primary alkyl (Et)	2386-64-3	E107829	Ethylmagnesium chloride	2.0 M solution in THF	EtMgCl: For ethyl installation and rapid construction as an “ethyl nucleophile” (aldehyde/ketone addition, epoxide ring-opening); can also trap electrophiles to form C–C bonds. Pre-made solution supports accurate dosing and scale-up.
Alkyl Grignard reagents | Primary alkyl (Et)	925-90-6	E107752	Ethylmagnesium bromide	3.0 M in diethyl ether	High-concentration EtMgBr (Et₂O): Suitable for scale-up and reduced solvent volume; commonly used for ethylation (carbonyl addition / CO₂ carboxylation / epoxide ring-opening). Strictly anhydrous and oxygen-free handling is required; titration is recommended to calibrate effective concentration.
Alkyl Grignard reagents | Primary alkyl (Et)	925-90-6	E130053	Ethylmagnesium bromide	2.0 M solution in THF	Mid–high concentration EtMgBr (THF): For carbonyl additions/ring-opening reactions needing stronger driving force; on scale-up, manage heat release and mixing/mass transfer—prefer dropwise addition into the substrate solution with temperature control.
Alkyl Grignard reagents | Primary alkyl (Et)	925-90-6	E107753	Ethylmagnesium bromide solution	1.0 M in THF	EtMgBr (1.0 M): Lower concentration improves dosing precision and selectivity control; often used for small-scale screening, control experiments, and precise equivalent additions in multistep sequences.
Alkyl Grignard reagents | Primary alkyl (Et)	925-90-6	E434580	Ethylmagnesium bromide solution	1.0 M in tert-butyl methyl ether	EtMgBr (MTBE): A relatively “less coordinating / more hydrophobic” solvent system that can reduce side reactions on some substrates (e.g., over-addition or coordination-driven effects); also a solvent option that can be easier to handle at scale.
Alkyl Grignard reagents | Primary alkyl (Et)	925-90-6	E434581	Ethylmagnesium bromide solution	3.4 M in 2-methyltetrahydrofuran	High-concentration EtMgBr (2-MeTHF): Suitable for scale-up and high-throughput charging; 2-MeTHF is often used as a more “engineering-friendly/greener” solvent alternative to reduce solvent usage and improve process window.
Alkyl Grignard reagents | Primary linear alkyl (n-Bu)	693-04-9	B433330	Butylmagnesium chloride solution	2.0 M in diethyl ether	n-BuMgCl: A classic strongly nucleophilic/strongly basic organomagnesium source for carbonyl addition (installing n-butyl), CO₂ carboxylation, and epoxide ring-opening; also used as an alkylmagnesium partner in Kumada coupling (Ni/Pd catalysis). Ether solutions are often viewed as comparatively “milder/more stable”.
Alkyl Grignard reagents | Primary linear alkyl (n-Bu)	693-04-9	B107759	n-Butylmagnesium chloride	2.0 M in THF	n-BuMgCl: For n-butyl installation (aldehyde/ketone addition, epoxide ring-opening homologation, CO₂ carboxylation, etc.); also a Kumada coupling alkylmagnesium source (Ni/Pd). THF coordination increases reactivity; on scale-up, manage exotherms via controlled addition and temperature control, and titrate to confirm effective concentration.
Alkyl Grignard reagents | Primary linear alkyl (n-Bu)	693-03-8	B304412	Butylmagnesium bromide	1.0 M in THF	n-BuMgBr: For n-butyl installation (aldehyde/ketone → alcohol; esters/acyl halides → alcohol/ketone depending on equivalents and temperature control). Stronger THF coordination often gives higher activity, suitable for low-temperature additions and rapid conversions.
Alkyl Grignard reagents | Branched primary alkyl (i-Bu)	5674-02-2	I137886	Isobutylmagnesium chloride	2.0 M in THF	i-BuMgCl: For installing isobutyl via carbonyl addition and epoxide ring-opening homologation; also an organomagnesium partner in Kumada coupling. Branched alkyls are useful for steric/hydrophobicity comparison in SAR.
Alkyl Grignard reagents | Branched primary alkyl (i-Bu)	5674-02-2	I140753	Isobutylmagnesium chloride	2.0 M solution in diethyl ether	i-BuMgCl (Et₂O): A milder solvent environment, suitable when THF coordination is problematic or improved storage stability is desired; often preferred as a more processable option for scale-up.
Alkyl Grignard reagents | Branched primary alkyl (i-Bu)	926-62-5	I121177	Isobutylmagnesium bromide solution	1.0 M in THF	i-BuMgBr: For isobutylation (carbonyl addition, CO₂ carboxylation, epoxide ring-opening); THF solutions are more reactive, fitting low-temperature fast additions and substrates needing higher activity.
Alkyl Grignard reagents | Secondary alkyl (sec-Bu)	15366-08-2	B110312	sec-Butylmagnesium chloride	2.0 M in THF	sec-BuMgCl: Among the more strongly basic/higher-reactivity alkylmagnesium reagents; besides standard carbonyl addition, it is also often used for halogen–magnesium exchange / substrate metalation followed by electrophile trapping (depending on substrate and temperature window).
Alkyl Grignard reagents | Secondary alkyl (sec-Bu)	922-66-7	B121189	sec-Butylmagnesium bromide	1 M in tetrahydrofuran	sec-BuMgBr: For secondary-alkyl installation and fast additions; also common in metalation/exchange-type operations requiring stronger driving force (use low temperature and strictly anhydrous conditions to suppress side reactions).
Alkyl Grignard reagents | Tertiary alkyl (t-Bu)	677-22-5	T684330	tert-Butylmagnesium chloride	1.7 M in THF	t-BuMgCl: Bulky, combining basicity and nucleophilicity; used to install tert-butyl (carbonyl addition) or as a strong base for substrate metalation/exchange operations (conditions are substrate-dependent). THF supports solubility and reaction rate.
Alkyl Grignard reagents | Tertiary alkyl (t-Bu)	677-22-5	B107834	tert-Butylmagnesium chloride	1.0 M in THF	t-BuMgCl (THF): Suitable when faster rates and better solubility are needed; for carbonyl addition or metalation steps, temperature and equivalents largely determine selectivity.
Alkyl Grignard reagents | Tertiary alkyl (t-Bu)	677-22-5	B107835	tert-Butylmagnesium chloride	2.0 M in diethyl ether	High-concentration t-BuMgCl (Et₂O): Suitable for scale-up and efficient charging; when used for tert-butylation or strong-base operations, control exotherms, addition rate, and stirring efficiency.
Alkyl Grignard reagents | Tertiary alkyl (t-Bu)	677-22-5	B777265	tert-Butylmagnesium chloride	1.5 M in diethyl ether	t-BuMgCl (Et₂O): Commonly used for tert-butyl installation / strong-base treatments; extremely sensitive to moisture/oxygen—use inert atmosphere, dry solvents, and titration to verify effective concentration.
Alkyl Grignard reagents | Cycloalkyl (Cyclohexyl)	931-51-1	C121232	Cyclohexylmagnesium chloride	2.0 M in diethyl ether	Cyclohexyl installation reagent: For carbonyl addition to build cyclohexyl-substituted alcohols; also used for CO₂ carboxylation and epoxide ring-opening. Cycloalkyl sterics and hydrophobicity are frequently used for structure–property comparisons (solubility, conformation, hydrophobic pocket occupancy).
Alkyl Grignard reagents | Cycloalkyl (Cyclohexyl)	931-51-1	C434593	Cyclohexylmagnesium chloride solution	1.3 M in THF/toluene (1:1)	THF/toluene mixed solvent: Common when balancing solubility and reactivity; used for cyclohexylation and metalation/addition operations, especially where substrate solubility or temperature control is critical.
Alkyl Grignard reagents | Cycloalkyl (Cyclohexyl)	931-51-1	C121233	Cyclohexylmagnesium chloride solution	1.0 M in 2-methyltetrahydrofuran	2-MeTHF is more process-oriented: For cyclohexyl installation and scale-up; 2-MeTHF is often chosen as an alternative to THF to improve process window and reduce solvent usage (still titrate to confirm effective concentration).

Table 2 | Unsaturated Grignard Reagents (Vinyl / Allyl / Alkynyl)

Category	CAS No.	Aladdin Cat. No.	Name	Specification / Purity	Product features & applications
Vinyl Grignard reagents | Vinyl	1826-67-1	V107233	Vinylmagnesium bromide	1.0 M in THF	Vinyl installation reagent: Commonly used for aldehyde/ketone addition to give allylic alcohol frameworks (vinylation); also serves as a vinylmagnesium partner for Kumada coupling (Ni/Pd catalysis) to construct C(sp²)–C bonds.
Vinyl Grignard reagents | Vinyl	3536-96-7	V107234	Chlorovinylmagnesium	1.6 M in THF	Vinyl installation reagent: Often used for carbonyl vinylation (aldehydes/ketones → allylic alcohol frameworks), and as a vinylmagnesium coupling partner to build C(sp²)–C bonds. A good starting point for rapid “vinyl fragment build-out / comparison”; maintain strictly anhydrous/oxygen-free conditions and add at low temperature to control selectivity.
Allyl Grignard reagents | Allyl	1730-25-2	A299170	Allylmagnesium bromide	1.0 M in THF	Classic allylation reagent: For allyl addition to aldehydes/ketones to prepare homoallylic alcohols; also used for epoxide ring-opening and downstream functionalization. THF solutions are relatively more reactive; low-temperature control helps suppress side reactions and manage regioselectivity.
Allyl Grignard reagents | Allyl	1730-25-2	A110229	Allylmagnesium bromide	1.0 M in diethyl ether	Allyl Grignard (Et₂O): Commonly used for carbonyl allylation and rapid allyl side-chain construction; ether solvents are often considered “milder/more traditional” and can favor stability and scale-up handling in some systems (still strictly anhydrous/oxygen-free).
Alkynyl Grignard reagents | Terminal alkynyl (ethynyl)	4301-14-8	E137848	Ethynylmagnesium bromide	0.5 M in THF	Ethynyl nucleophile: Used to build propargylic alcohols (carbonyl addition), epoxide ring-opening to homologated propargylic alcohols, and CO₂ carboxylation to alkynoic acids. Terminal-alkynyl systems are more susceptible to acidic impurities—require stricter drying and low-temperature control.
Alkynyl Grignard reagents | Alkyl-substituted alkynyl (1-propynyl)	16466-97-0	P137858	1-Propynylmagnesium bromide solution	0.5 M in THF	Pre-made alkynyl Grignard: For nucleophilic addition to aldehydes/ketones to give substituted propargylic alcohols (installing –C≡CCH₃); also applicable to epoxide ring-opening homologation and CO₂ carboxylation. Moisture/oxygen sensitive—typically added dropwise at low temperature to manage exotherms.

Table 3 | Aryl / Benzyl Grignard Reagents (Ar / Bn)

Category	CAS No.	Aladdin Cat. No.	Name	Specification / Purity	Product features & applications
Aryl Grignard reagents | Phenyl (Ph)	100-59-4	P107833	Phenylmagnesium chloride	2.0 M in tetrahydrofuran	PhMgCl: A classic aryl nucleophile for arylation (aldehyde/ketone addition), CO₂ carboxylation to aromatic acids, and Kumada coupling to build C(sp²)–C bonds. Suitable for rapid aryl-fragment build-out and comparisons.
Aryl Grignard reagents | Phenyl (Ph)	100-58-3	P103163	Phenylmagnesium bromide	1.0 M in THF	PhMgBr: Similar to PhMgCl for aryl installation/coupling; reactivity and solubility windows may differ in certain systems and can serve as an alternative during condition screening.
Aryl Grignard reagents | p-Tolyl	4294-57-9	T767097	p-Tolylmagnesium bromide	0.5 M in THF	Aryl nucleophile: For installing p-tolyl (addition to aldehydes/ketones to give aryl alcohols; CO₂ carboxylation to aryl acids, etc.); also a common arylmagnesium partner for Kumada coupling (Ni/Pd) to build aryl–aryl or aryl–vinyl bonds.
Aryl Grignard reagents | p-Tolyl	4294-57-9	T121101	p-Tolylmagnesium bromide	1.0 M in THF	Same aryl Grignard (higher concentration): Suitable for coupling/addition scale-up. Moisture/oxygen sensitive; arylmagnesium reagents have limited tolerance toward certain functional groups (e.g., labile halides, acidic N–H/O–H), so assess functional-group window first.
Benzyl Grignard reagents | Benzyl (Bn)	6921-34-2	B141028	Benzylmagnesium chloride	2.0 M in THF	BnMgCl: For benzyl installation (carbonyl addition to benzyl-substituted alcohols; CO₂ carboxylation; C–C formation with selected electrophiles). Benzyl fragments are frequently used for hydrophobic anchoring/protecting-group routes and SAR controls.
Benzyl Grignard reagents | Benzyl (Bn)	6921-34-2	B106922	Benzylmagnesium chloride	1.0 M in THF	Benzyl Grignard (lower concentration): Supports more precise dosing and selectivity control; suitable for low-temperature additions to sensitive substrates and for small-scale screening/controls.
Benzyl Grignard reagents | Benzyl (Bn)	1589-82-8	B684852	Benzylmagnesium bromide	0.5 mol/L in THF	BnMgBr: For benzylation (carbonyl addition, electrophile trapping, etc.). Lower concentration is preferable for exotherm-sensitive systems or where fine control of equivalents is required.
Benzyl Grignard reagents | Benzyl (Bn)	1589-82-8	B115959	Benzylmagnesium bromide	1 mol/L in THF	BnMgBr (1 M): Commonly used for benzyl installation and route scale-up validation. Pay attention to substrate functional-group tolerance (acidic N–H/O–H and labile halides often require protection or route changes).

Table 4 | Exchange/Metalation Tools and Functionalized Organomagnesium Reagents (Turbo / TMSCH₂–)

Category	CAS No.	Aladdin Cat. No.	Name	Specification / Purity	Product features & applications
Alkyl Grignard reagents | Secondary alkyl (i-Pr) / often used for halogen–Mg exchange	1068-55-9	I107831	Isopropylmagnesium chloride	2.0 M in THF	i-PrMgCl: Beyond standard additions/base use, it is more commonly used as an entry reagent for halogen–magnesium exchange and metalation (especially in combination with LiCl and related systems), enabling rapid generation of aryl/heteroaryl magnesium intermediates for electrophile trapping or coupling.
Halogen–Mg exchange / metalation | Turbo Grignard (i-PrMgCl·LiCl)	745038-86-2	I121226	Isopropylmagnesium chloride–lithium chloride complex	1.3 M in THF	Typical “Turbo Grignard”: Widely used for halogen–Mg exchange (aryl/heteroaryl bromides/iodides, etc.) and controlled metalation to rapidly form organomagnesium intermediates, which can then trap electrophiles (carbonyls, boronate precursors, sulfonates, etc.) or enter coupling. Compared with standard i-PrMgCl, it is often faster and more controllable, suitable for low-temperature work with sensitive substrates.
Functionalized Grignard reagent | Silylmethyl (TMSCH₂–)	13170-43-9	T121180	(Trimethylsilyl)methylmagnesium chloride solution	1.0 M in diethyl ether	TMSCH₂MgCl: A common “silyl-stabilized methide equivalent” that adds to carbonyls to form β-silyl alcohols; subsequent Peterson elimination and related steps enable alkene construction/homologation, supporting one-carbon extension and controlled desilyl transformations in synthesis.
Functionalized Grignard reagent | Silylmethyl (TMSCH₂–)	13170-43-9	T299176	(Trimethylsilyl)methylmagnesium chloride solution	1 mol/L in tetrahydrofuran	TMSCH₂MgCl (THF): THF solutions are typically faster and offer better solubility; used in sequences of carbonyl addition → β-silyl alcohol → elimination/desilylation, serving as an entry point to a “transformable methyl/one-carbon module.”

Note: The above items are representative Aladdin products. For more specifications, please refer to the product list at the end of the document, or search the Aladdin website using the product name / CAS / catalog number.

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